JP2019172936A - Composition for heat radiation member, heat radiation member, and electronic device - Google Patents

Abstract

To provide a composition capable of forming a heat radiation member having further controllability of high thermal conductivity and thermal expansion coefficient, and the heat radiation member.SOLUTION: The composition for heat radiation member has: a first coupling agent 11; a thermal conductive first inorganic filler 1 bound to a terminal of the first coupling agent 11; a second coupling agent 12; a thermal conducive second inorganic filler 2 bound to a terminal of the second coupling agent 12; a bi- or higher functional polymerizable compound 22 bound to another terminal of the second coupling agent 12; a third coupling agent 13; and a thermal conductive third inorganic filler 3 bound to a terminal of the third coupling agent 13. The first coupling agent 11 and the polymerizable compound 22 have groups capable of binding each other respectively, the third coupling agent 13 and the polymerizable compound 22 have groups capable of binding each other respectively, and the third inorganic filler 3 is a nitride whisker.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for a heat dissipation member. In particular, the present invention relates to a heat radiating member composition capable of forming a heat radiating member that can dissipate heat by efficiently conducting and transmitting heat generated in an electronic device and control a coefficient of thermal expansion.

  In recent years, in semiconductor elements for power control, such as hybrid cars and electric cars, and CPUs for high-speed computers, it has been desired to increase the thermal conductivity of package materials so that the temperature of internal semiconductors does not become too high. That is, the ability to effectively release the heat generated from the semiconductor chip to the outside is important. In addition, due to the increase in operating temperature, thermal distortion occurs due to the difference in coefficient of thermal expansion between the materials used in the package, and there is a problem of a decrease in life due to peeling of the wiring.

  As a method for solving such a heat dissipation problem, development of a heat dissipation member in which an inorganic material and a resin are combined to increase heat conductivity has been performed. Patent Document 1 discloses an embodiment in which an inorganic material is not added to a resin in a composite of an organic material and an inorganic material, but an inorganic material is connected to each other, that is, a coupling agent and a bifunctional or higher functional polymerizable compound. A composite material having extremely high thermal conductivity and capable of controlling the coefficient of thermal expansion is disclosed by bonding an inorganic material through a coupling agent or by coupling inorganic materials through a coupling agent ( Paragraph 0007).

International Publication No. 2016/031888

As described above, the heat dissipation member is always required to have higher thermal conductivity and controllability of the thermal expansion coefficient with the development of electronic equipment.
Then, this invention makes it a subject to provide the composition and heat dissipation member which can form the heat dissipation member which has the high thermal conductivity of the further perpendicular | vertical direction (thickness direction), and the controllability of a thermal expansion coefficient.

  The inventors of the present invention have made extensive studies in order to obtain further high thermal conductivity and controllability of the thermal expansion coefficient in a heat dissipation member in which inorganic materials are connected to each other via a coupling agent and a polymerizable compound. As a result, it has been found that by further combining whisker with a combination of an inorganic material, a coupling agent and a polymerizable compound, further high thermal conductivity in the vertical direction (thickness direction) and controllability of the thermal expansion coefficient can be obtained. The present invention has been completed.

The heat radiating member composition according to the first aspect of the present invention comprises, for example, as shown in FIG. 2, a first coupling agent 11; a thermally conductive material coupled to one end of the first coupling agent 11. A first inorganic filler 1, a second coupling agent 12, a thermally conductive second inorganic filler 2 bonded to one end of the second coupling agent 12, and the second coupling agent 12. A bifunctional or higher functional polymerizable compound 22 bonded to the other end of: a third coupling agent 13; and a thermally conductive third inorganic filler 3 bonded to one end of the third coupling agent 13; The first coupling agent 11 and the polymerizable compound 22 each have a group capable of binding to each other, and the third coupling agent 13 and the polymerizable compound 22 are groups capable of binding to each other. Each having a third inorganic filler 3 is a nitride whiskers. The “one end” and “the other end” may be edges or ends of the molecule shape, and may or may not be both ends of the long side of the molecule.
If comprised in this way, in the heat radiating member formed from the said composition for heat radiating members, a 3rd inorganic filler (nitride whisker) can also be couple | bonded with a 2nd inorganic filler through a coupling agent and a polymeric compound. The thermal conductivity can be further improved by further bonding with the nitride whiskers. This is presumably because the number of paths suitable for propagation of phonons, which are the main elements of heat conduction, can be increased by coupling with nitride whiskers.

For example, as shown in FIG. 4, the composition for a heat radiating member according to the second aspect of the present invention has a first coupling agent 11; a thermally conductive material coupled to one end of the first coupling agent 11. A first inorganic filler 1; a second coupling agent 12; a thermally conductive second inorganic filler 2 bonded to one end of the second coupling agent 12; a third coupling agent 13; A thermally conductive third inorganic filler 3 bonded to one end of the third coupling agent 13, wherein the first coupling agent and the second coupling agent can be bonded to each other; The third coupling agent and the second coupling agent each have a group capable of binding to each other, and the third inorganic filler is a nitride whisker.
If comprised in this way, in the heat radiating member formed from the said composition for heat radiating members, a 3rd inorganic filler (nitride whisker) can also be couple | bonded with a 2nd inorganic filler through a coupling agent. The thermal conductivity can be further improved by further bonding with the nitride whiskers. This is presumably because the number of paths suitable for propagation of phonons, which are the main elements of heat conduction, can be increased by coupling with nitride whiskers.

The composition for heat dissipation members according to the third aspect of the present invention is the composition for heat dissipation members according to the first aspect or the second aspect of the present invention, wherein the first inorganic filler and the second inorganic filler are used. The average particle diameter of the filler is 0.1 to 500 μm, and the nitride whiskers are acicular, fibrous, or particulate.
If comprised in this way, the shape of a whisker can be made preferable. In particular, whiskers that are crushed into particles are preferred.

The composition for heat radiating members according to the fourth aspect of the present invention is the composition for heat radiating members according to any one of the first aspect to the third aspect of the present invention. And 0.1 to 10 parts by mass of the third inorganic filler with respect to 100 parts by mass of the total amount of the second inorganic filler.
If comprised in this way, even if the addition amount of a nitride whisker is a small amount (about several%), thermal conductivity can be improved remarkably.

The composition for heat radiating members according to the fifth aspect of the present invention is the composition for heat radiating members according to any one of the first aspect to the fourth aspect of the present invention. And the second inorganic filler is independently at least one selected from boron nitride, aluminum nitride, carbon nitride boron, boron carbide, graphite, carbon fiber, carbon nanotube, alumina, and cordierite.
If comprised in this way, the thermal conductivity of an inorganic filler is high, and a thermal expansion coefficient is very small or negative, and the target composition for heat radiating members is obtained by compounding with these.

The composition for heat radiating members according to the sixth aspect of the present invention is the composition for heat radiating members according to any one of the first to fifth aspects of the present invention, wherein the third inorganic filler is used. Is at least one selected from aluminum nitride whiskers and boron nitride whiskers.
If comprised in this way, a composition can be comprised using the whisker suitable for the improvement of thermal conductivity.

The composition for heat radiating members according to the seventh aspect of the present invention is the composition for heat radiating members according to any one of the first aspect to the sixth aspect of the present invention. The organic compound, the high molecular compound, or the inorganic compound which is not couple | bonded with the said 2nd inorganic filler and the said 3rd inorganic filler is further included.
With this configuration, when the size of the first, second, and third inorganic fillers is increased in order to improve the thermal conductivity, and the void ratio increases accordingly, the voids are combined. It can be filled with a compound that is not present, and heat conductivity, water vapor blocking performance, and the like can be improved.

［式（１−１）〜（１−２）中、Ｒ^ｂは、それぞれ独立して、水素、ハロゲン、−ＣＦ_３、または炭素数１〜５のアルキルであり、ｑは０または１である。］

［式（１−４）〜（１−６）中、Ｒ^７〜Ｒ^１０は、それぞれ独立して、水素、または炭素数１〜２０のアルキレンである。］
このように構成すると、重合性化合物の構造は反応部位が少なく、熱による影響を受けにくいため、放熱部材は高耐熱性を有することができる。 A composition for a heat dissipation member according to an eighth aspect of the present invention is the composition for a heat dissipation member according to any one of the first aspect, the third aspect to the seventh aspect of the present invention. The polymerizable compound before being bonded to the ring agent is at least one bifunctional or higher-polymerizable non-liquid crystal compound represented by the following formula (1).
R ^a —R ⁶ —O— (Rx) _n —O—R ¹¹ —R ^a (1)
[In the above formula (1),
Each R ^a is independently any of the following formulas (1-1) to (1-2), amino, vinyl, carboxylic anhydride residues, or any polymerizable group containing these structures;
Rx is any one of the following formulas (1-3) to (1-6);
n is an integer from 1 to 3;
R ⁶ and R ¹¹ are each independently a single bond or alkylene having 1 to 20 carbon atoms. ]

[In the formulas (1-1) to (1-2), R ^b is independently hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbon atoms, and q is 0 or 1. . ]

[In formulas (1-4) to (1-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms. ]
If comprised in this way, since the structure of a polymeric compound has few reaction sites and it is hard to receive the influence by a heat | fever, a heat radiating member can have high heat resistance.

The composition for heat radiating members according to the ninth aspect of the present invention is the composition for heat radiating members according to the eighth aspect of the present invention, wherein the first coupling agent, the second coupling agent, The third coupling agent is a silane coupling agent represented by the following formula (6).
^{_{(R 1 -O) j -Si (}} R 5) 3-j - (R 2) k - (R 3) m - (R 4) n -Ry (6)
[In the above formula (6),
R ¹ is H-, or CH _3- (CH ₂ ) _{0 -4-} ;
R ² is — (CH ₂ ) _0-3- O—;
R ³ is 1,3-phenylene, 1,4-phenylene, naphthalene-2,6-diyl, or naphthalene-2,7-diyl;
R ⁴ _{is, - (NH) 0~1 - (} CH 2) 0~3 - a and;
R ⁵ is H— or CH ₃ — (CH ₂ ) _0-7 —;
Ry is oxiranyl, oxetanyl, amino, vinyl, carboxylic anhydride residue, or any polymerizable group containing these structures;
j is an integer from 0 to 3;
k is an integer from 0 to 1;
m is an integer from 0 to 1;
n is an integer from 0 to 1;
Formula (6) includes at least one of R ³ and R ⁴ . ]
If comprised in this way, since the structure of a coupling agent has few reaction sites and is hard to be influenced by heat, a heat radiating member can have high heat resistance.

A composition for a heat dissipation member according to a tenth aspect of the present invention is the composition for a heat dissipation member according to any one of the first aspect, the third aspect to the seventh aspect of the present invention. The polymerizable compound before being bonded to the ring agent is at least one of a bifunctional or higher polymerizable liquid crystal compound represented by the following formula (2).
Ra-Z- (AZ) m-Ra (2)
[In the formula (2),
Each Ra is independently a group capable of binding to the other end of the first coupling agent, the second coupling agent, or the third coupling agent;
A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, arbitrary —CH ₂ — may be replaced with —O—, optional —CH═ may be replaced with —N═, and optional hydrogen is halogen, carbon number 1 Or an alkyl halide having 1 to 10 carbon atoms or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH═CH—, or —C≡C—;
Each Z is independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —CH ₂ — represents —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═N—, -N = CH-, -N = N-, -N (O) = N-, or -C≡C-, and any hydrogen may be replaced by halogen;
m is an integer of 1-6. ]
If comprised in this way, a polymeric compound is thermosetting, can be hardened without being influenced by the quantity of a filler, and is further excellent in heat resistance. In addition, the molecular structure has symmetry and linearity, which is considered advantageous for phonon propagation.

［上記式（３）中、
Ｒ^１およびＲ^２は、それぞれ独立して、水素、ハロゲン、または炭素数１〜３のアルキルであり；
ｍは２〜４の整数であり、ｎは１〜３の整数であり、ｐは２〜４の整数であり、ｑは１〜３の整数であり、ｍ＋ｎ＝５であり、ｐ＋ｑ＝５であり；
Ａは、単結合、炭素数１〜１０のアルキレン、シクロヘキシレン、シクロヘキセニレン、フェニレン、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクト−１，４−ジイル、ビシクロ［３．１．０］ヘキス−３，６−ジイル、４，４’−（９−フルオレニリデン）ジフェニレン、アダマンタンジイル、または、ビアダマンタンジイルであり、
炭素数１〜１０のアルキレンにおいて、任意の水素は−ＣＨ_３で置き換えられてもよく、
シクロヘキシレン、シクロヘキセニレン、フェニレン、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクト−１，４−ジイル、ビシクロ［３．１．０］ヘキス−３，６−ジイル、４，４’−（９−フルオレニリデン）ジフェニレン、アダマンタンジイル、または、ビアダマンタンジイルにおいて、任意の−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は、−Ｎ＝で置き換えられてもよく、任意の水素は、ハロゲン、炭素数１〜１０のアルキル、または炭素数１〜１０のハロゲン化アルキルで置き換えられてもよく、
任意の水素と置き換えられたアルキルにおいて、任意の−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく；
Ｚ^１、Ｚ^２は、それぞれ独立して、単結合、または炭素数１〜２０のアルキレンであり、
該アルキレンにおいて、任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよい。］
［上記式（４）中、
ｘは２以上の整数であり；
環Ｂは、ベンゼン、ナフタレン、アントラセン、フェナレン、フェナントレン、フルオレン、９，９‐ジフェニルフルオレン、アダマンタン、またはビアダマンタンであり、
環Ｂにおいて、任意の−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は、−Ｎ＝で置き換えられてもよく、任意の水素は、ハロゲン、炭素数１〜３のアルキル、または炭素数１〜３のハロゲン化アルキルで置き換えられてもよく、
環Ｂの炭素数１〜３のアルキル、または炭素数１〜３のハロゲン化アルキルにおいて、任意の−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよい。］
このように構成すると、２官能以上のヒドロキシ基を有する重合性化合物のうち特に好ましい化合物を用いて放熱部材用組成物を構成することができる。これらの化合物は熱硬化性であり、フィラーの量に影響を受けずに硬化させることができる。また分子構造は、対称性、直線性を有するため、フォノンの伝播に有利であると考えられる。 A composition for a heat radiating member according to an eleventh aspect of the present invention is the composition for a heat radiating member according to any one of the first aspect, the third aspect to the seventh aspect of the present invention. The polymerizable compound before binding to the ring agent is at least one polymerizable non-liquid crystal compound having a bifunctional or higher functional hydroxy group represented by the following formula (3) or (4).

[In the above formula (3),
R ¹ and R ² are each independently hydrogen, halogen, or alkyl having 1 to 3 carbon atoms;
m is an integer of 2 to 4, n is an integer of 1 to 3, p is an integer of 2 to 4, q is an integer of 1 to 3, m + n = 5, and p + q = 5 Yes;
A represents a single bond, alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′-(9-fluorenylidene) diphenylene, adamantanediyl, or biadamantanediyl And
In the alkylene having 1 to 10 carbon atoms, arbitrary hydrogen may be replaced with —CH ₃ ;
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, In bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′-(9-fluorenylidene) diphenylene, adamantanediyl or biadamantanediyl, any —CH ₂ — is —O—. Any -CH = may be replaced by -N =, and any hydrogen is replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons May be
In the alkyl substituted with any hydrogen, any —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, any —CH ₂ — may be replaced with —O—, —S—, —CO—, —COO—, or —OCO—, and any hydrogen may be replaced with a halogen. . ]
[In the above formula (4),
x is an integer greater than or equal to 2;
Ring B is benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, 9,9-diphenylfluorene, adamantane, or biadamantane;
In Ring B, any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any hydrogen may be a halogen, a carbon number of 1 to 3 alkyl, or an alkyl halide having 1 to 3 carbon atoms,
In the alkyl having 1 to 3 carbon atoms or the alkyl halide having 1 to 3 carbon atoms in the ring B, arbitrary —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. May be. ]
When comprised in this way, the composition for heat radiating members can be comprised using the especially preferable compound among the polymeric compounds which have a bifunctional or more functional hydroxyl group. These compounds are thermosetting and can be cured without being affected by the amount of filler. In addition, the molecular structure has symmetry and linearity, which is considered advantageous for phonon propagation.

The heat radiating member according to the twelfth aspect of the present invention is a cured product of the composition for a heat radiating member according to any one of the first to eleventh aspects of the present invention.
If comprised in this way, a thermal radiation member has a coupling | bonding between inorganic fillers, and can have very high thermal conductivity.

An electronic apparatus according to a thirteenth aspect of the present invention includes the heat dissipating member according to the twelfth aspect of the present invention; and an electronic device having a heat generating part, so that the heat dissipating member contacts the heat generating part. Arranged in the electronic device.
If comprised in this way, the heat which generate | occur | produced in the electronic device can be efficiently conducted with the heat radiating member which has high thermal conductivity. Further, by making the thermal expansion coefficient in the surface direction close to the thermal expansion coefficient of a semiconductor element such as copper wiring, silicon, or silicon nitride attached to the heat dissipation member, a device that is difficult to be peeled off by heat cycle can be manufactured.

  The heat dissipating member formed from the composition for heat dissipating member of the present invention has extremely high thermal conductivity and controllability of the thermal expansion coefficient in combination with the nitride whisker. In addition, it has excellent properties such as chemical stability, heat resistance, hardness and mechanical strength.

In the heat radiating member of this invention, it is a conceptual diagram which shows the coupling | bonding of inorganic fillers by making boron nitride into an example. 1st inorganic filler 1 couple | bonded with the 1st coupling agent 11 which the composition for heat radiating members by one embodiment of this invention couple | bonded, and the polymeric compound 22 and the 2nd coupling agent 12 couple | bonded It is an image figure of the 3rd inorganic filler 3 couple | bonded with the 2nd inorganic filler 2 and the 3rd coupling agent 13. FIG. In the heat dissipating member of the present invention, the state in which the second inorganic filler 2, the third inorganic filler 3, and the second inorganic filler 2 are bonded via a coupling agent and a polymerizable compound is shown as an example of boron nitride. It is a conceptual diagram. The 1st inorganic filler 1 couple | bonded with the 1st coupling agent 11 and the 2nd inorganic couple | bonded with the 2nd coupling agent 12 which the composition for heat radiating members by other embodiment of this invention contains It is an image figure of the 3rd inorganic filler 3 couple | bonded with the filler 2 and the 3rd coupling agent 13. FIG. 6 is a graph showing measurement results obtained by the thermomechanical analyzer of Example 1. FIG. 6 is a graph showing measurement results obtained by the thermomechanical analyzer of Example 2. 6 is a graph showing measurement results obtained by the thermomechanical analyzer of Example 3. 6 is a graph showing measurement results obtained by the thermomechanical analyzer of Example 4. 6 is a graph showing measurement results obtained by the thermomechanical analyzer of Comparative Example 1. 6 is a graph showing a measurement result by a thermomechanical analyzer of Comparative Example 2. 10 is a graph showing measurement results obtained by the thermomechanical analyzer of Comparative Example 3. 10 is a graph showing a measurement result by a thermomechanical analyzer of Comparative Example 4. It is a SEM image (1000 times) of an aluminum nitride whisker. It is a SEM image (1000 times) of the aluminum nitride whisker which was crushed into particles.

  Embodiments of the present invention will be described below with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same or similar reference numerals, and redundant description is omitted. Further, the present invention is not limited to the following embodiments.

Terms used in this specification are as follows.
“Liquid crystal compound” and “liquid crystal compound” are compounds that exhibit a liquid crystal phase such as a nematic phase or a smectic phase.

In a phrase such as “any —CH ₂ — in alkyl may be replaced by —O—” or “any —CH ₂ CH ₂ — may be replaced by —CH═CH—, etc.” The meaning is shown in the following example. For example, the group in which any —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— includes C ₃ H ₇ O—, CH ₃ —O— (CH ₂ ) _{2. -, CH 3 -O-CH 2} -O- , and the like. Similarly, as the group in which any —CH ₂ CH ₂ — in C ₅ H ₁₁ — is replaced by —CH═CH—, H ₂ C═CH— (CH ₂ ) ₃ —, CH ₃ —CH═CH Examples of the group in which arbitrary —CH ₂ — is replaced by —O—, such as — (CH ₂ ) ₂ —, include CH ₃ —CH═CH—CH ₂ —O—. Thus, the term “arbitrary” means “at least one selected without distinction”. In consideration of the stability of the compound, CH ₃ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other than CH ₃ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other. Is preferred.

  The phrase “any hydrogen may be replaced by halogen, alkyl having 1 to 10 carbon atoms, or alkyl halide having 1 to 10 carbon atoms” with respect to ring A is, for example, 2 of 1,4-phenylene. , 3, 5 and 6 positions are substituted with a substituent such as fluorine or methyl group, and the substituent is "C1-10 halogenated alkyl" Examples of the method include examples such as a 2-fluoroethyl group and a 3-fluoro-5-chlorohexyl group.

“Compound (1)” means a polymerizable compound represented by the following formula (1), which will be described later, and may mean at least one compound represented by the following formula (1). “Composition for heat radiating member” means a composition containing at least one compound selected from the compound (1) or other polymerizable compounds. When one compound (1) has a plurality of A, any two A may be the same or different. When two or more compounds (1) have A, arbitrary two A may be the same or different. This rule also applies to other symbols and groups such as ^Ra and Z.

[Composition for heat dissipation member]
The composition for heat radiating members of the present invention is a composition that forms a heat radiating member by bonding inorganic fillers via a coupling agent and a bifunctional or higher polymerizable compound, and includes nitride whiskers. FIG. 1 shows an example of bonding when boron nitride is used as the inorganic filler. When boron nitride (h-BN) is treated with a coupling agent, boron nitride does not have a reactive group in the plane of the particle, and thus a plurality of coupling agents are bonded only to the periphery thereof. Thus, the coupling | bonding with a some coupling agent is formed with respect to an inorganic filler. Furthermore, the coupling agent can also be combined with a polymerizable compound. Therefore, a plurality of bonds can be formed between boron nitrides by coupling the coupling agents bonded to boron nitride with a polymerizable compound, as shown in FIG.
Thus, since the phonon can be directly propagated by bonding the inorganic fillers via the coupling agent and the polymerizable compound, the heat dissipation member formed from the composition for heat dissipation member of the present invention is The composite material has extremely high thermal conductivity and directly reflects the coefficient of thermal expansion of the inorganic component.

The composition for a heat dissipation member according to the first embodiment of the present invention includes, for example, as shown in FIG. 2, a first coupling agent 11; and heat conduction combined with one end of the first coupling agent 11. First inorganic filler 1 having a conductive property; second coupling agent 12; heat-conductive second inorganic filler 2 bonded to one end of the second coupling agent 12; and second coupling. A bifunctional or higher functional polymerizable compound 22 bonded to the other end of the agent 12; a third coupling agent 13; and a thermally conductive third inorganic filler bonded to one end 13 of the third coupling agent 13. 3 and; The first coupling agent 11 and the polymerizable compound 22 each have a group capable of bonding to each other. The third coupling agent 13 and the polymerizable compound 22 each have a group capable of bonding to each other. The third inorganic filler 3 is a nitride whisker.
When the other end of the first coupling agent 11 is bonded to the polymerizable compound 22 due to the curing of the heat radiating member composition, a bond between the first inorganic filler 1 and the second inorganic filler 2 is formed. (FIG. 1).
Further, as shown in FIG. 2, the third inorganic filler includes the third inorganic filler 3 (nitride whisker) combined with the third coupling agent 13, and therefore, by curing the heat radiating member composition, The other end of the third coupling agent 13 can also form a bond with the polymerizable compound 22, and a bond between the second inorganic filler 2 and the third inorganic filler 3 is formed.
In FIG. 2, one bond is taken as an example for explanation. However, when an inorganic filler is modified with a coupling agent, a plurality of coupling agent molecules are usually bonded to the inorganic filler. Therefore, as shown in FIG. 3, the plurality of third coupling agents 13 bonded to the third inorganic filler 3 form bonds with different polymerizable compounds 22.

For example, as shown in FIG. 4, the composition for a heat radiating member according to the second embodiment of the present invention includes a first coupling agent 11; and heat conduction combined with one end of the first coupling agent 11. First inorganic filler 1, second coupling agent 12, thermally conductive second inorganic filler 2 bonded to one end of the second coupling agent 12, and third coupling agent And a thermally conductive third inorganic filler 3 bonded to one end of the third coupling agent 13. The first coupling agent 11 and the second coupling agent 12 each have a group capable of binding to each other. The third coupling agent 13 and the second coupling agent 12 have groups that can be bonded to each other. The third inorganic filler 3 is a nitride whisker.
When the other end of the first coupling agent 11 is bonded to the second coupling agent 12 by the curing of the heat radiating member composition, the bond between the first inorganic filler 1 and the second inorganic filler 2 is Formed (FIG. 1).
Further, as shown in FIG. 4, the third inorganic filler includes the third inorganic filler 3 (nitride whisker) combined with the third coupling agent 13, and therefore, by curing the heat radiating member composition, The other end of the third coupling agent 13 can also form a bond with the second coupling agent 12, and a bond between the second inorganic filler 2 and the third inorganic filler 3 is formed. .

式（１−１）〜（１−２）中、Ｒ^ｂはそれぞれ独立して、水素、ハロゲン、−ＣＦ_３、または炭素数１〜５のアルキルであり、ｑは０または１である。

式（１−４）〜（１−６）中、Ｒ^７〜Ｒ^１０は、それぞれ独立して、水素、または炭素数１〜２０のアルキレンである。 As the bifunctional or higher polymerizable compound, one having a group capable of forming a bond with a coupling agent is selected.
<A bifunctional or higher polymerizable non-liquid crystal compound>
The bifunctional or higher functional polymerizable compound may be a non-liquid crystalline compound. Examples of the non-liquid crystalline bifunctional or higher polymerizable compound include a polymerizable compound represented by the following formula (1).
R ^a —R ⁶ —O— (Rx) _n —O—R ¹¹ —R ^a (1)
In the above formula (1),
Each R ^a is independently any of the following formulas (1-1) to (1-2), amino, vinyl, carboxylic anhydride residues, or any polymerizable group containing these structures;
Rx is naphthalene-2,6-diyl, or naphthalene-2,7-diyl, biphenyl-2,2 ′, biphenyl-2,4 represented by the following formulas (1-3) to (1-6) ', One of biphenyl-3,3';
n is an integer from 1 to 3;
R ⁶ and R ¹¹ are each independently a single bond or alkylene having 1 to 20 carbon atoms.

In formulas (1-1) to (1-2), R ^b is independently hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons, and q is 0 or 1.

In formulas (1-4) to (1-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbons.

In the above formula (1), each R ^a can be independently bonded to the other end of the first coupling agent, the other end of the second coupling agent, or the other end of the third coupling agent. Any group may be used. For example, in addition to the polymerizable groups represented by the above formulas (1-1) to (1-2), cyclohexene oxide, phthalic anhydride, or succinic anhydride can be exemplified, but not limited thereto.
The polymerizable compound represented by the formula (1) has few reactive sites in its structure and is not easily affected by heat. On the other hand, the structure was found to be excellent in phonon propagation. Therefore, the heat radiating member formed from the composition for heat radiating member can have high heat resistance with high heat conductivity.

<Bifunctional or higher polymerizable liquid crystal compound>
The bifunctional or higher polymerizable compound may be a liquid crystal compound. Examples of the bifunctional or higher functional polymerizable compound having liquid crystallinity include a polymerizable liquid crystal compound represented by the following formula (2).
The polymerizable liquid crystal compound has a liquid crystal skeleton and a polymerizable group, and has high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, and the like. This compound (2) tends to be uniform when mixed with other liquid crystalline compounds or polymerizable compounds.
R ^a -Z- (AZ) _m -R ^a (2)

By appropriately selecting the terminal group R ^a , the ring structure A, and the bonding group Z of the compound (2), physical properties such as a liquid crystal phase expression region can be arbitrarily adjusted. The effects of the terminal group R ^a , the ring structure A and the bonding group Z on the physical properties of the compound (2) and preferred examples thereof will be described below.

・ Terminal group R ^a
The terminal group R ^a has the same meaning as R ^a defined in the above formula (1).

・ Ring structure A
When at least one ring in the ring structure A of the compound (2) is 1,4-phenylene, the orientational order parameter and the magnetic anisotropy are large. When at least two rings are 1,4-phenylene, the temperature range of the liquid crystal phase is wide and the clearing point is high. When at least one hydrogen on the 1,4-phenylene ring is substituted with cyano, halogen, —CF ₃ or —OCF ₃ , the dielectric anisotropy is high. When at least two rings are 1,4-cyclohexylene, the clearing point is high and the viscosity is low.

  In the above formula (2), preferable A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2, 5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro- 1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine- 3,6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluor Ren-2,7-diyl, 9-ethyl-2,7-diyl, 9-fluoro-2,7-diyl, etc. 9,9-difluoro-2,7-diyl.

  The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally identical, the latter is not illustrated. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

  In the above formula (2), more preferable A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro. -1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and the like. Particularly preferred A is 1,4-cyclohexylene and 1,4-phenylene.

・ Linking group Z
The linking group Z of the compound (2) is a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, When —CF═CF— or — (CH ₂ ) ₄ —, in particular, a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH— or — (CH _{2) 4} -, the viscosity is reduced. Further, when the bonding group Z is —CH═CH—, —CH═N—, —N═CH—, —N═N— or —CF═CF—, the temperature range of the liquid crystal phase is wide. Further, when the bonding group Z is alkyl having about 4 to 10 carbon atoms, the melting point is lowered.

In the above formula (2), preferred Z is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O—, —O (CH _{2) 3 -, - (CH} 2) 2 COO -, - OCO (CH 2) 2 -, - CH = CH-COO -, - OCO-CH = CH- , and the like.

In the above formula (2), more preferable Z is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, — OCF ₂ —, —CH═CH—, —C≡C— and the like can be mentioned. Particularly preferred Z is a single bond, — (CH ₂ ) ₂ —, —COO— or —OCO—.

  The more the compound (2) has more rings, the more difficult it is to soften at higher temperatures, so it is preferable as a heat dissipation material. However, since the molding becomes difficult when the softening temperature is higher than the polymerization temperature, a balance between both is achieved according to the purpose. It is preferable. In the present specification, basically, a 6-membered ring and a condensed ring including a 6-membered ring are regarded as a ring, and for example, a 3-membered ring, a 4-membered ring or a 5-membered ring alone is not regarded as a ring. A condensed ring such as a naphthalene ring or a fluorene ring is regarded as one ring.

The compound (2) may be optically active or optically inactive. When the compound (2) is optically active, the compound (2) may have an asymmetric carbon or an axial asymmetry. The configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located at either ^Ra or A, and when it has an asymmetric carbon, the compatibility of the compound (2) is good. When the compound (2) has axial asymmetry, the twist-inducing force is large. In addition, the light application property may be any.
As described above, a compound having desired physical properties can be obtained by appropriately selecting the terminal group R ^a , the type of the ring structure A and the bonding group Z, and the number of rings.

式（２−１）〜（２−２）中、Ｒ^ｂがそれぞれ独立して、水素、ハロゲン、−ＣＦ_３、または炭素数１〜５のアルキルであり、ｑは０または１である。 Compound (2) can also be represented by the following formula (2a) or (2b).

PY- (AZ) _m -R ^a (2a)
PY- (AZ) _m -YP (2b)

In the above formula (2a) and (2b), A, Z, R a has the same meaning as ^A, Z, ^{R a} as defined by the above formula (2), P is the following formula (2-1) to (2 2) represents a polymerizable group represented by 2), cyclohexene oxide, phthalic anhydride, or succinic anhydride, Y represents a single bond or alkylene having 1 to 20 carbon atoms, preferably alkylene having 1 to 10 carbon atoms, In alkylene, any —CH ₂ — may be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —CH═CH—. Particularly preferred Y is alkylene in which —CH ₂ — at one or both ends of alkylene having 1 to 10 carbon atoms is replaced by —O—. m is an integer of 1-6, preferably an integer of 2-6, more preferably an integer of 2-4.

In formulas (2-1) to (2-2), R ^b is independently hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons, and q is 0 or 1.

  Examples of the preferred compound (2) include the following compounds (a-1) to (a-10), (b-1) to (b-16), (c-1) to (c-16), (D-1) to (d-15), (e-1) to (e-15), (f-1) to (f-14), (g-1) to (g-20). . In the formula, * represents an asymmetric carbon.

In the chemical formulas (a-1) to (g-20), R ^a , P and Y are as defined in the above formulas (2a) and (2b).
Z ¹ is each independently a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —C≡C—, —C≡C—COO—, —OCO—C≡C—, —C≡C—CH═CH—, —CH═ CH—C≡C—, —CH═N—, —N═CH—, —N═N—, —OCF ₂ — or —CF ₂ O—. The plurality of Z ¹ may be the same or different.

In the above chemical formulas (a-1) to (g-20), Z ² each independently represents — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH. ₂ O—, —OCH ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═. CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —C≡C—, —C≡C—COO—, —OCO—C≡C—, — C≡C—CH═CH—, —CH═CH—C≡C—, —CH═N—, —N═CH—, —N═N—, —OCF ₂ — or —CF ₂ O—.

In the above chemical formulas (a-1) to (g-20), Z ³ each independently represents a single bond, alkyl having 1 to 10 carbon atoms, — (CH ₂ ) _a —, —O (CH ₂ ) _{a. O -, - CH 2 O -} , - OCH 2 -, - O (CH 2) 3 -, - (CH 2) 3 O -, - COO -, - OCO -, - CH = CH -, - CH = CHCOO _{-, - OCOCH = CH -,} - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - CF = CF -, - C≡C -, - CH = N -, - N = CH-, —N═N—, —OCF ₂ — or —CF ₂ O—, and the plurality of Z ³ may be the same or different. a is an integer of 1-20.

  In the above chemical formulas (a-1) to (g-20), X represents substitution of 1,4-phenylene and fluorene-2,7-diyl in which arbitrary hydrogen may be replaced by halogen, alkyl, or alkyl fluoride. Group, halogen, alkyl or alkyl fluoride.

The more preferable aspect of the said compound (2) is demonstrated. More preferable compound (2) has the following characteristics in the following formula (2a) or (2b).

PY- (AZ) _m -R ^a (2a)
PY- (AZ) _m -YP (2b)

In the above formula, A, Y, Z, ^Ra and m are as defined above, and P represents a polymerizable group represented by the following formulas (2-1) to (2-2). In the case of the above formula (2b), two P represent the same polymerizable group (2-1) to (2-2), two Y represent the same group, and two Y are symmetrical. Join.

<Polymerizable non-liquid crystal compound having a bifunctional or higher hydroxy group>
The bifunctional or higher functional polymerizable compound may be a non-liquid crystalline compound having a hydroxy group. Examples of the polymerizable compound having a non-liquid crystalline bifunctional or higher functional hydroxyl group include at least one polymerizable compound represented by the following formula (3) or (4).

In the above formula (3),
R ¹ and R ² are each independently hydrogen, halogen, or alkyl having 1 to 3 carbon atoms;
m is an integer of 2 to 4, n is an integer of 1 to 3, p is an integer of 2 to 4, q is an integer of 1 to 3, m + n = 5, and p + q = 5 Yes;
A represents a single bond, alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] Octo-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′-(9-fluorenylidene) diphenylene, adamantanediyl, or biadamantanediyl Yes,
In the alkylene having 1 to 10 carbon atoms, arbitrary hydrogen may be replaced with —CH ₃ ;
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, In bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′-(9-fluorenylidene) diphenylene, adamantanediyl or biadamantanediyl, any —CH ₂ — is —O—. Any -CH = may be replaced by -N =, and any hydrogen is replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons May be
In the alkyl substituted with any hydrogen, any —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, any —CH ₂ — may be replaced with —O—, —S—, —CO—, —COO—, or —OCO—, and any hydrogen may be replaced with a halogen. .

In the above formula (3), A is a single bond, alkylene having 1 to 10 carbon atoms, phenylene, or phenylene in which any hydrogen is replaced with a halogen or a methyl group; Z ¹ and Z ² are each independently Te single _{bond, - (CH 2) a -} , - O -, - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O -, - COO -, - _{OCO -, - CH 2 CH 2} -COO -, - OCO-CH 2 CH 2 -, - OCF 2 - or _-CF 2 is O-, it is preferred that the a is an integer from 1 to 20.

上記式（３−１）〜（３−１１）において、Ｒ^１、Ｒ^２、ｍ、ｎ、ｐ、ｑ、Ｚ^１、Ｚ^２は、式（３）と同一であり；Ｒ^３〜Ｒ^６３は、それぞれ独立して、水素、ハロゲン、炭素数１〜１０のアルキル、または炭素数１〜１０のハロゲン化アルキルである。 Examples of particularly preferred compound (3) include compounds (3-1) to (3-11) shown below.

In the above formulas (3-1) to (3-11), R ¹ , R ² , m, n, p, q, Z ¹ and Z ² are the same as those in the formula (3); R ^{3 to} R ⁶³ Are each independently hydrogen, halogen, alkyl having 1 to 10 carbons, or halogenated alkyl having 1 to 10 carbons.

In the above formula (4),
x is an integer greater than or equal to 2;
Ring B is benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, 9,9-diphenylfluorene, adamantane, or biadamantane,
In Ring B, any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any hydrogen may be a halogen, a carbon number of 1 to 3 alkyl, or an alkyl halide having 1 to 3 carbon atoms,
In the alkyl having 1 to 3 carbon atoms or the alkyl halide having 1 to 3 carbon atoms in the ring B, arbitrary —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. May be.

  In the above formula (4), ring B is preferably benzene, naphthalene, 9,9-diphenylfluorene, or adamantane.

上記式（４−１）〜（４−１０）において、ｘは、式（４）と同一である。上記式（４−１）〜（４−１０）の環において、ヒドロキシ基の位置は任意である。 Examples of particularly preferred compound (4) include compounds (4-1) to (4-10) shown below.

In the above formulas (4-1) to (4-10), x is the same as in formula (4). In the rings of the above formulas (4-1) to (4-10), the position of the hydroxy group is arbitrary.

<Polymerizable liquid crystal compound having a bifunctional or higher functional hydroxy group>
The bifunctional or higher functional polymerizable compound may be a liquid crystalline compound having a hydroxy group. Examples of the polymerizable compound having a bifunctional or higher functional hydroxy group having liquid crystallinity include at least one polymerizable compound represented by the following formula (5). The compound (5) has a liquid crystal skeleton and a bifunctional or higher functional hydroxy group, and has high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, and the like. This compound (5) tends to be uniform when mixed with other liquid crystalline compounds or polymerizable compounds.

In the above formula (5), s is an integer of 0 to 4, t is an integer of 1 or more, and u is an integer of 1 or more.
By appropriately selecting the ring C, the bonding group W, and the bonding group Y of the compound (5), the physical properties such as the liquid crystal phase developing region can be arbitrarily adjusted. The effects of ring C, linking group W and linking group Y on the physical properties of compound (5) and preferred examples thereof will be described below.

・ Linking group Y
In the above formula (5), each of the bonding groups Y independently represents a single bond or alkylene having 1 to 20 carbon atoms, preferably alkylene having 1 to 10 carbon atoms. In the alkylene having 2 to 20 carbon atoms, Any —CH ₂ — that is not bound to a hydroxy group may be replaced with —O—, —S—, —CO—, —COO— or —OCO—, and any hydrogen is replaced with a halogen. Also good. When Y is a linear alkylene, the temperature range of the liquid crystal phase is wide and the viscosity is small. On the other hand, when Y is branched alkylene, compatibility with other liquid crystal compounds is good.

・ Ring C
When at least one ring in the ring C of the compound (5) is 1,4-phenylene, the orientational order parameter and the magnetic anisotropy are large. When at least two rings are 1,4-phenylene, the temperature range of the liquid crystal phase is wide and the clearing point is high. When at least one hydrogen on the 1,4-phenylene ring is substituted with cyano, halogen, —CF ₃ or —OCF ₃ , the dielectric anisotropy is high. When at least two rings are 1,4-cyclohexylene, the clearing point is high and the viscosity is low.

  In the above formula (5), preferable ring C is 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2. , 5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro -1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine -3,6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethyl Rufuruoren 2,7-diyl, 9-ethyl-2,7-diyl, 9-fluoro-2,7-diyl, etc. 9,9-difluoro-2,7-diyl.

  The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally identical, the latter is not illustrated. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

  In the above formula (5), more preferable C is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro. -1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and the like. Particularly preferred A is 1,4-cyclohexylene and 1,4-phenylene.

・ Linking group W
The bonding group W of the compound (5) is independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, — When CH═CH—, —CF═CF— or — (CH ₂ ) ₄ —, in particular, a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH - or - _{(CH 2) 4} - when it, the viscosity decreases. When the bonding groups W are independently —CH═CH—, —CH═N—, —N═CH—, —N═N— or —CF═CF—, the temperature range of the liquid crystal phase Is wide. Further, when the bonding group W is alkylene having about 4 to 10 carbon atoms, the melting point is lowered.

In the above formula (5), preferred linking group W is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH _2. —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— and the like can be mentioned.

In the above formula (5), more preferable bonding group W is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , —OCF ₂ —, —CH═CH—, —C≡C— and the like. The particularly preferred bonding group W is a single bond, — (CH ₂ ) ₂ —, —COO— or —OCO—.

  When the compound (5) has 3 or less rings, the viscosity is low, and when it has 3 or more rings, the clearing point is high.

The compound (5) may be optically active or optically inactive. When the compound (5) is optically active, the compound (5) may have an asymmetric carbon or an axial asymmetry. The configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located in any of the ring C, the linking group W, and the linking group Y. When the asymmetric carbon is present, the compatibility of the compound (5) is good. When the compound (5) has axial asymmetry, the twist-inducing force is large. In addition, the light application property may be any.
As described above, a compound having desired physical properties can be obtained by appropriately selecting the type of ring C, bonding group W, bonding group Y, and number of rings.

  Specific examples (f-1-1) to (f-14-2) are shown below as preferred compounds of the compound (2b) and the compound (5).

-Method for synthesizing compounds (1), (2), (3), (4), and (5) The above compounds (1), (2), (3), (4), and (5) are combined with known methods in organic synthetic chemistry. Can be synthesized. Methods for introducing the desired end groups, ring structures and linking groups into the starting materials are described, for example, by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Books such as Wily & Sons, Inc., Organic Reactions, John Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen) It is described in. Japanese Patent Application Laid-Open No. 2006-265527 may be referred to.

Bifunctional or higher polymerizable compounds (hereinafter sometimes simply referred to as “polymerizable compounds”) are polymerizable compounds other than the polymerizable compounds represented by the above formulas (1), (2), (3), (4), and (5). It may be. For example, the diglycidyl ether of polyether, the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, the diglycidyl ether of biphenol, or the compound of formula (2) (5) lacks linearity and exhibits liquid crystallinity. Examples of the compounds that were not used.
The polymerizable compound can be synthesized by combining known methods in organic synthetic chemistry.

  The polymerizable compound used in the present invention preferably has a bifunctional or higher functional group, including a case of a trifunctional or higher functional group or a tetrafunctional or higher functional group. Furthermore, a compound having a functional group at both ends of the long side of the polymerizable compound is preferable because it can form a linear bond.

<First and second inorganic fillers>
Examples of the first inorganic filler and the second inorganic filler include nitrides, carbides, and carbon materials. The first inorganic filler and the second inorganic filler may be the same or different.
For the first inorganic filler and the second inorganic filler, boron nitride, boron carbide, boron nitride carbon, graphite, carbon fiber, carbon nanotube are used as inorganic fillers having high thermal conductivity and a very small or negative coefficient of thermal expansion. Cordierite or the like may be used. Alternatively, an inorganic filler having a high thermal conductivity and a positive thermal expansion coefficient, such as aluminum nitride or alumina, may be used for either the first or second inorganic filler.
Boron nitride, aluminum nitride, silicon nitride, silicon carbide, graphite, carbon fiber, and carbon nanotube are preferable. In particular, hexagonal boron nitride (h-BN) and graphite are preferable. Boron nitride and graphite are preferable because they have a very high thermal conductivity in the plane direction, and boron nitride has a low dielectric constant and high insulation. For example, it is preferable to use plate-like crystal boron nitride because the plate-like structure is easily oriented along the mold by the flow and pressure of the raw material during molding and curing.

  The kind, shape, size, addition amount, and the like of the inorganic filler can be appropriately selected according to the purpose. When the heat dissipating member needs insulation, an inorganic filler having conductivity may be used as long as the desired insulation is maintained. Examples of the shape of the inorganic filler include a plate shape, a spherical shape, an amorphous shape, a fiber shape, a rod shape, and a tubular shape. The polymerizable compound preferably has a shape and length that can efficiently bond these inorganic fillers.

The average particle size of the first inorganic filler and the second inorganic filler is preferably 0.1 to 500 μm. More preferably, it is 1-100 micrometers. When it is 0.1 μm or more, the thermal conductivity is good, and when it is 200 μm or less, the filling rate can be increased.
In the present specification, the average particle size is based on particle size distribution measurement by a laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle size by the wet method using the analysis by Franhofer diffraction theory and Mie's scattering theory, the diameter where the large side and the small side are equivalent (volume basis) The median diameter was used.

<Third inorganic filler>
The third inorganic filler is a nitride whisker. Aluminum nitride whiskers and boron nitride whiskers are preferred.
The shape of the nitride whisker is not particularly limited. Generally, the fibrous thing (FIG. 13) marketed may be used, a fibrous whisker may be crushed and used, and it may be crushed to a particulate form (FIG. 14).
When a silane coupling agent is bonded to aluminum nitride whisker or boron nitride whisker, as shown in FIG. 3, a bond is more densely formed with respect to the first inorganic filler and the second inorganic filler. It is suitable for propagation, and the formed heat dissipation member can obtain high thermal conductivity.

<Coupling agent>
The coupling agent to be bonded to the inorganic filler is selected from those having a group that reacts with the functional group of the polymerizable compound. For example, when the polymerizable compound has an oxiranyl group, one having an amine group or the like is preferable. For example, Silac Ace (trade names) S310, S320, S330, and S360 are available from JNC Corporation, and KBM903 and KBE903 are available from Shin-Etsu Chemical Co., Ltd. When the polymerizable compound has an amine group or a hydroxy group, a coupling agent having an oxiranyl group or the like is preferable. Examples of the products manufactured by JNC Corporation include Sila Ace (trade names) S510 and S530. The amount of modification of the coupling agent with respect to the inorganic filler is preferably 0.2 to 20% by weight, more preferably 1 from the viewpoint that a heat radiating member excellent in balance with high thermal conductivity and high heat resistance can be easily obtained. -10% by weight.

When the compound of the said Formula (1) is used as a bifunctional or more polymeric compound, it is preferable to use the silane coupling agent represented by following formula (6) as a coupling agent.

^{_{(R 1 -O) j -Si (}} R 5) 3-j - (R 2) k - (R 3) m - (R 4) n -Ry (6)

In the above formula (6),
R ¹ is H-, or CH _3- (CH ₂ ) _{0 -4-} ;
R ² is — (CH ₂ ) _0-3- O—;
R ³ is 1,3-phenylene, 1,4-phenylene, naphthalene-2,6-diyl, or naphthalene-2,7-diyl;
R ⁴ _{is, - (NH) 0~1 - (} CH 2) 0~3 - a and;
R ⁵ is H— or CH ₃ — (CH ₂ ) _0-7 —;
Ry is oxiranyl, oxetanyl, amino, vinyl, carboxylic anhydride residue, or any polymerizable group containing these structures;
j is an integer from 0 to 3;
k is an integer from 0 to 1;
m is an integer from 0 to 1;
n is an integer from 0 to 1;
Formula (6) includes at least one of R ³ and R ⁴ .

<Additional filler>
The composition for heat radiating members of the present invention may further contain an inorganic filler and contain a plurality of types of inorganic fillers. For example, you may add the inorganic filler which has a thermal expansion coefficient different from a 1st inorganic filler, a 2nd inorganic filler, and a 3rd inorganic filler. In addition, when the first inorganic filler and the second inorganic filler are two-dimensional plate-like or one-dimensional linear, if only these are combined, the physical properties of the combined heat radiating member composition are greatly different. A direction arises. By adding an additional filler, there is an advantage that the orientation of the first and second inorganic fillers is relaxed and anisotropy is reduced. Furthermore, when the thermal expansion coefficient of the first and second inorganic fillers is very small or negative, by adding an additional filler having a positive thermal expansion coefficient, the thermal expansion coefficient is more accurately adjusted from negative to positive depending on the mixing ratio. It becomes possible to control. Although there is no restriction | limiting in the inorganic filler used for an additional filler, It is desirable that it is a thing with high heat conductivity.

  Additional fillers include silicon carbide, aluminum nitride, silicon nitride, diamond, silicon, beryllia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide with high thermal conductivity and positive thermal expansion. , Cerium oxide, yttrium oxide, tin oxide, holmium oxide, bismuth oxide, cobalt oxide, calcium oxide, magnesium hydroxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, Mention may be made of inorganic fillers and metal fillers such as tungsten, molybdenum and stainless steel.

<Other components>
The composition for a heat dissipation member of the present invention further includes an organic compound that is not bonded to the first inorganic filler, the second inorganic filler, and the third inorganic filler, that is, does not contribute to bonding (for example, a polymerizable compound or a high Molecular compound) and a polymerization initiator, a solvent, and the like.

<Polymerizable compound not bonded>
The composition for a heat radiating member may include a polymerizable compound (in this case, not necessarily bifunctional or higher) that is not bonded to an inorganic filler as a constituent element. As such a polymerizable compound, a compound that does not lower the film formability and the mechanical strength is preferable. This polymerizable compound is classified into a compound having no liquid crystallinity and a compound having liquid crystallinity. Examples of the polymerizable compound having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, and the like. As for the content, first, it is desirable to prepare a composition for a heat dissipation member that does not contain an unbonded polymerizable compound, measure its porosity, and add an amount of the polymerizable compound that can fill the void.

<Polymer compound not bonded>
The composition for a heat radiating member may include a polymer compound that is not bonded to an inorganic filler as a constituent element. As such a polymer compound, a compound that does not lower the film-forming property and mechanical strength is preferable. The polymer compound may be any polymer compound that does not react with the first, second, and third inorganic fillers and the polymerizable compound. For example, a polyolefin resin, a polyvinyl resin, a polyamide resin, a polyitaconic acid resin, and the like. Is mentioned. As for the content, it is desirable to prepare a composition for a heat radiation member that does not contain an unbonded polymer compound, measure its porosity, and add an amount of the polymer compound that can fill the void.

<Non-polymerizable liquid crystalline compound>
The composition for a heat radiating member may contain a liquid crystal compound having no polymerizable group as a constituent element. Examples of such non-polymerizable liquid crystal compounds are described in Licris, a database of liquid crystal compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). By polymerizing a composition for a heat dissipation member containing a non-polymerizable liquid crystal compound, for example, a composite material of a polymer of the compound (2) and a liquid crystal compound can be obtained. In such a composite material, a non-polymerizable liquid crystal compound is present in a polymer network like a polymer dispersed liquid crystal. Preferably, it is a liquid crystalline compound having such a characteristic that it does not have fluidity in the temperature range to be used. After the first, second, and third fillers are cured, the first, second, and third fillers may be combined by a method in which the first, second, and third fillers are injected into the voids in a temperature region that exhibits an isotropic phase. The filler may be polymerized by mixing an amount of liquid crystalline compound calculated so as to fill the voids in advance.

<Polymerization initiator>
The composition for heat radiating members may contain a polymerization initiator as a constituent element. As the polymerization initiator, for example, a radical photopolymerization initiator, a cationic photopolymerization initiator, a thermal radical polymerization initiator, or the like may be used depending on the components of the composition and the polymerization method.
Preferred initiators for thermal radical polymerization include, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide. Oxide (DTBPO), t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), etc. Can be mentioned.

<Solvent>
The composition for heat radiating members may contain a solvent. When a component that needs to be polymerized is contained in the composition, the polymerization may be performed in a solvent or without a solvent. A composition containing a solvent may be applied onto a substrate by, for example, a spin coating method and then photopolymerized after removing the solvent. Further, after photocuring, it may be heated to an appropriate temperature and post-treated by heat curing.
Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopentanone. , Cyclohexanone, PGMEA and the like. The said solvent may be used individually by 1 type, or may mix and use 2 or more types.
It should be noted that there is not much meaning in limiting the ratio of the solvent used during the polymerization, and it may be determined for each case in consideration of the polymerization efficiency, the solvent cost, the energy cost, and the like.

<Others>
A stabilizer may be added to the heat dissipating member composition for easy handling. As such a stabilizer, known ones can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
Furthermore, an inorganic compound (such as an oxide) may be added as an additive in order to adjust the viscosity and color of the heat radiating member composition. For example, titanium oxide for making white, carbon black for making black, and silica fine powder for adjusting viscosity can be mentioned. Further, an additive may be added to further increase the mechanical strength. For example, fibers or long molecules such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide can be used as inorganic fibers and cloth such as glass and carbon fiber, or polymer additives.

[Production method]
Hereinafter, the method for producing the heat radiating member composition and the method for producing the heat radiating member from the heat radiating member composition will be specifically described. In the following, the case where a bifunctional or higher functional polymerizable compound is included in the bond between inorganic fillers is described, but the same applies when the bifunctional or higher functional polymerizable compound is not included (coupling agents are directly bonded to each other). It can be manufactured by the method.

<Manufacturing composition for heat dissipation member>
The ratio of the first and second inorganic fillers, the coupling agent, and the bifunctional or higher functional polymerizable compound depends on the amount of the coupling agent to be combined with the inorganic filler to be used. When boron nitride is used as the first and second inorganic fillers, boron nitride has no reactive groups on the surface and has reactive groups only on the side surfaces. It is preferable that a coupling agent is bonded to the few reactive groups, and a polymerizable compound having the same number as or slightly larger than the number of the reactive groups is bonded.

-Applying the coupling treatment The first inorganic filler is treated with the first coupling agent, and the first inorganic filler and one end of the first coupling agent are combined to form a modified filler A. A known method can be used for the coupling treatment.
As an example, first, an inorganic filler and a coupling agent are added to a solvent. Stir using a stirrer or the like and then dry. After solvent drying, heat treatment is performed under vacuum conditions using a vacuum dryer or the like. A solvent is added to the inorganic filler and pulverized by ultrasonic treatment. The solution is separated and purified using a centrifuge. After discarding the supernatant, a solvent is added and the same operation is repeated several times. The inorganic filler (modified filler A) subjected to the coupling treatment after purification using an oven is dried.
Similarly, a modified filler C obtained by treating a third inorganic filler (nitride whisker) with a third coupling agent (the third coupling agent may be the same as the first coupling agent). May be different).

The other end of the second coupling agent of the second inorganic filler (which may be the same as or different from the modified filler A) treated with the second coupling agent that is modified with the polymerizable compound A bifunctional or higher functional polymerizable compound is bound to. The filler modified with the polymerizable compound in this way is referred to as a modified filler B.
As an example, the inorganic filler subjected to the coupling treatment and the polymerizable compound are mixed using an agate mortar or the like and then kneaded using a biaxial roll or the like. Thereafter, separation and purification are performed by sonication and centrifugation.

-Mixing The modified filler A, the modified filler B, and the modified filler C are weighed so that the weight ratio of only the first inorganic filler and the second inorganic filler is 1: 1, for example, and mixed in an agate mortar or the like. Then, it mixes using a biaxial roll etc. and obtains the composition for heat radiating members.
The mixing ratio (weight ratio) of the first inorganic filler and the second inorganic filler (without modification) is, for example, 1: 1 when the bonding group that forms the bond between the modified filler A and the modified filler B is amine: epoxy. The ratio is preferably 1 to 1:30, more preferably 1: 3 to 1:20. The mixing ratio is determined by the number of terminal linking groups that form the bond between the modified filler A and the modified filler B. For example, if it is a secondary amine, it can react with two oxiranyl groups. It's okay. Moreover, since the oxiranyl group side may be ring-opened, it is preferable to use more than the amount calculated from an epoxy equivalent.
The mixing ratio of the third inorganic filler (nitride whisker, no modification) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the first inorganic filler and the second inorganic filler. More preferably, it is 1-7 mass parts. When it is 0.1 part by mass or more, a structure having high thermal conductivity is obtained, and when it is 10 parts by mass or less, the heat dissipation member is formed at a high density.

<Manufacturing heat dissipation member>
As an example, the method to manufacture the film as a heat radiating member using the composition for heat radiating members is demonstrated. The heat radiating member composition is sandwiched between hot plates using a compression molding machine, and cured by compression molding. Further, post-curing is performed using an oven or the like to obtain the heat radiating member of the present invention. The pressure at the time of compression molding is preferably 50 to 200 kgf / cm ² , more preferably 70 to 180 kgf / cm ² . Basically, the pressure during curing is preferably high. However, it is preferable that the pressure is appropriately changed depending on the fluidity of the mold and the target physical properties (which direction of thermal conductivity is important) and an appropriate pressure is applied.

Hereinafter, a method for producing a film as a heat radiating member using a composition for a heat radiating member containing a solvent will be specifically described.
First, the composition for heat radiating members is apply | coated on a board | substrate, a solvent is dried and removed, and the coating-film layer with a uniform film thickness is formed. Examples of the coating method include spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and the like.
The solvent can be removed by drying, for example, by air drying at room temperature, drying on a hot plate, drying in a drying furnace, blowing hot air or hot air, and the like. The conditions for removing the solvent are not particularly limited, and it may be dried until the solvent is almost removed and the fluidity of the coating layer is lost.

  Examples of the substrate include metal substrates such as copper, aluminum, and iron; inorganic semiconductor substrates such as silicon, silicon nitride, gallium nitride, and zinc oxide; glass substrates such as alkali glass, borosilicate glass, and flint glass; alumina; Inorganic insulating substrates such as aluminum nitride; polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, polyethyleneterephthalate, polybutyleneterephthalate , Polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, Acetyl cellulose or partially saponified product thereof, epoxy resin, phenol resin, and the like plastic film substrate such as norbornene resins.

  The film substrate may be a uniaxially stretched film or a biaxially stretched film. The film substrate may be subjected to surface treatment such as saponification treatment, corona treatment, or plasma treatment in advance. In addition, you may form the protective layer which is not attacked by the solvent contained in the said composition for heat radiating members on these film substrates. Examples of the material used as the protective layer include polyvinyl alcohol. Furthermore, an anchor coat layer may be formed in order to improve the adhesion between the protective layer and the substrate. Such an anchor coat layer may be any inorganic or organic material as long as it improves the adhesion between the protective layer and the substrate.

  As conditions for curing the composition for heat dissipation member by thermal polymerization, the thermosetting temperature is in the range of room temperature to 350 ° C., preferably room temperature to 250 ° C., more preferably 50 ° C. to 200 ° C., and the curing time is 5 Second to 50 hours, preferably 1 minute to 30 hours, more preferably 5 minutes to 20 hours. After the polymerization, it is preferable to slowly cool in order to suppress stress strain and the like. In addition, reheating treatment may be performed to reduce strain and the like.

<Group capable of bonding to each other>
The bond between the coupling agent and the bifunctional or higher-polymerizable compound or the bond between the coupling agents is not particularly limited as long as it is a combination of groups that can be bonded to each other. As long as a bond can be formed, a combination of different ones or the same combination may be used. For example, a combination in which one has an amino group and the other has an epoxy group may be used.
As described above, combinations of groups that can be bonded to each other include oxiranyl group and amino group, vinyl groups, methacryloxy groups, carboxy group or carboxylic dianhydride group and amino group, imidazole group and oxiranyl group, and hydroxy group. A combination of an oxiranyl group and the like can be mentioned, but is not limited thereto. A combination with high heat resistance is more preferable.

  Bifunctional or higher polymerizable compounds may have different functional groups. For example, the first inorganic filler is coupled with a first silane coupling agent having an amino group. Next, the second silane coupling agent having a vinyl group is modified with a polymerizable compound having a vinyl group and an epoxy group at the terminals, and then the second inorganic filler is coupled with the second silane coupling agent. To process. During the curing treatment, the amino group of the first coupling agent and the epoxy group of the polymerizable compound are bonded.

[Heat dissipation member]
The heat radiating member according to the third embodiment of the present invention is formed by molding a cured product obtained by curing the composition for a heat radiating member according to the first and second embodiments. It is. This cured product has high thermal conductivity and a negative or very small positive coefficient of thermal expansion, and is excellent in chemical stability, heat resistance, hardness, mechanical strength, and the like. The mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength, and the like.

The heat radiating member of this invention is formed from the said composition for heat radiating members, and uses it in shapes, such as a sheet | seat, a film, a thin film, a fiber, a molded object. Preferred shapes are plates, sheets, films and thin films. In addition, the thickness of the heat radiating member in this specification is 2 micrometers or more, Preferably it is 5 micrometers-5 mm, More preferably, it is 10 micrometers-2 mm, More preferably, it is 20 micrometers-1 mm. What is necessary is just to change thickness suitably according to a use.
The heat dissipating member of the present invention is suitable for, for example, a heat dissipating substrate, a heat dissipating plate (planar heat sink), a heat dissipating sheet, a heat dissipating film, a heat dissipating coating, a heat dissipating adhesive, and a heat dissipating molded product.

[Electronics]
An electronic apparatus according to a fourth embodiment of the present invention includes the heat dissipation member according to the third embodiment and an electronic device having a heat generating portion. A heat radiating member is arrange | positioned at an electronic device so that the said heat-emitting part may be contacted. The shape of the heat dissipation member may be any of a heat dissipation electronic substrate, a heat dissipation plate, a heat dissipation sheet, a heat dissipation film, a heat dissipation adhesive, a heat dissipation molded product, and the like.
For example, a semiconductor element can be given as an electronic device. The heat dissipation member of the present invention has high heat resistance and high insulation in addition to high thermal conductivity. Therefore, it is particularly effective for an insulated gate bipolar transistor (IGBT) that requires a more efficient heat dissipation mechanism because of high power among semiconductor elements. An IGBT is one of semiconductor elements and is a bipolar transistor in which a MOSFET is incorporated in a gate portion, and is used for power control. Electronic devices equipped with IGBTs include high-power inverter main conversion elements, uninterruptible power supply devices, AC motor variable voltage variable frequency control devices, railway vehicle control devices, electric vehicles such as hybrid cars and electric cars, IH A cooker can be mentioned.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the contents described in the following examples.

・３−グリシドキシプロピルトリメトキシシラン、ＪＮＣ（株）製、（商品名）サイラエース（登録商標）Ｓ５１０

＜２官能以上の重合性化合物＞
・重合性オキシラニル化合物：ＪＮＣ（株）製、下記式（２−Ａ）
下記式（２−Ａ）は、特許第５０８４１４８号公報に記載の方法で合成することができる。

・三菱ケミカル（株）製、（商品名）ｊＥＲ ＹＸ４０００Ｈ

・４，４’−（プロパン−２，２−ジイル）ジフェノール、和光純薬工業（株）製、（慣用名）ビスフェノールＡ

＜硬化促進剤＞
・２−エチル−４−メチル−１Ｈ−イミダゾール、和光純薬工業（株）製、（一般名）２−エチル−４−メチル−イミダゾール

The component materials used in the examples of the present invention are as follows.
<Inorganic filler>
Boron nitride: h-BN particles, manufactured by Momentive Performance Materials Japan (commercial), (trade name) PolarTherm PTX-25
<Whisker>
Aluminum nitride whisker (fibrous): U-MaP, AlN whisker Aluminum nitride whisker (particulate): U-MaP, crushed AlN whisker <Silane coupling agent>
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by JNC, (trade name) Silaace (registered trademark) S320

3-glycidoxypropyltrimethoxysilane, manufactured by JNC Corporation, (trade name) Silaace (registered trademark) S510

<Bifunctional or higher polymerizable compound>
Polymerizable oxiranyl compound: manufactured by JNC Corporation, the following formula (2-A)
The following formula (2-A) can be synthesized by the method described in Japanese Patent No. 5084148.

・ Mitsubishi Chemical Co., Ltd., (trade name) jER YX4000H

・ 4,4 ′-(propane-2,2-diyl) diphenol, manufactured by Wako Pure Chemical Industries, Ltd. (common name) bisphenol A

<Curing accelerator>
2-ethyl-4-methyl-1H-imidazole, manufactured by Wako Pure Chemical Industries, Ltd. (generic name) 2-ethyl-4-methyl-imidazole

Below, the preparation example of a heat radiating member is shown.
[Example 1]
-Preparation of silane coupling agent-treated boron nitride particles 15 g of boron nitride particles (PTX-25 manufactured by Momentive Performance Materials Japan) and 2.25 g of silane coupling agent S320 are added to 100 mL of toluene, and 500 rpm using a stirrer. The resulting mixture was dried at 40 ° C. for 4 hours. Furthermore, it heat-processed for 5 hours under vacuum conditions using the vacuum dryer set to 120 degreeC after solvent drying. The obtained particles were designated as modified filler A.

Preparation of silane coupling agent-treated aluminum nitride whisker 0.116 g of aluminum nitride whisker (AlN whisker manufactured by U-Map) into 0.012 g of silane coupling agent S320 / pure water mixed solution (weight ratio 1: 1) In addition, after mixing well, the resulting mixture was dried at 40 ° C. for 4 hours. Furthermore, after the solvent was dried, it was heat-treated for 5 hours under vacuum conditions using a vacuum dryer set at 120 ° C. The obtained particles were designated as modified filler C.

  1.0 g of each of the modified filler A and the compound represented by the formula (2-A) was weighed out and mixed at 120 ° C. for 10 minutes using two rolls (IMC-AE00 type manufactured by Imoto Seisakusho Co., Ltd.). This weight ratio is the number of epoxy groups with which the amino group of the modified filler A is sufficiently reacted and the amount that both are sufficiently kneaded on the two rolls. After adding the obtained mixture to 45 mL of tetrahydrofuran and stirring sufficiently, the insoluble matter was allowed to settle with a centrifuge (High-speed cooling centrifuge CR22, manufactured by Hitachi Koki Co., Ltd., 4,000 rpm × 10 min × 25 ° C.). The solution containing the amount of unreacted epoxy dissolved by decantation was removed. Thereafter, 45 mL of acetone was added, and the same operation as described above was performed. Further, the same operation was repeated in the order of tetrahydrofuran and acetone. Particles obtained by drying the insoluble matter were designated as modified filler B.

・ Mixing and molding / curing of modified filler A, modified filler B and modified filler C 0.17 g of modified filler A, 0.53 g of modified filler B, and 0.035 g of modified filler C were weighed. Taken and mixed.
The obtained mixture was sandwiched between stainless steel plates using a metal frame so as not to be oxidized, and pressurized to 40 MPa using a compression molding machine (IMC-19EC manufactured by Imoto Seisakusho Co., Ltd.) set at 150 ° C. for 30 minutes. Pre-curing was performed by continuing the heating state. That is, when the mixture spreads between the stainless steel plates, since BN is plate-like particles, the particles and the stainless steel plates were oriented in parallel. The amount of the metal frame and the sample was adjusted so that the thickness of the sample was about 500 μm. Further, curing was carried out using a vacuum oven at 80 ° C. for 3 hours and at 200 ° C. for 14 hours. Let the sample obtained by this operation be a heat radiating member.

-Evaluation of thermal expansion coefficient A test piece of 4x20 mm was cut out from the obtained sample, and the thermal expansion coefficient (measured with a SII TMA-SS6100 thermomechanical analyzer) was in the range of 50 to 200 ° C. Asked. The length and temperature range of the test piece were appropriately adjusted according to the shape of the sample to be measured.

-Evaluation of thermal conductivity The thermal conductivity was measured in advance with the specific heat of the heat radiating member (measured with Rigaku DSC-8231, DSC input compensation type differential scanning calorimeter) and the specific gravity (Mettler Toledo specific gravity meter AG204). The thermal conductivity in the vertical direction is obtained by multiplying the value by the thermal diffusivity obtained by an ai-Phase Mobile 1u thermal diffusivity measuring device manufactured by I-Phase Co., Ltd. Asked.

[Example 2]
A crushed AlN whisker manufactured by U-Map Co., Ltd. was used for the aluminum nitride of the modified filler C. Except this, it produced and evaluated similarly to Example 1. FIG.

[Example 3]
As a substitute for the compound represented by the formula (2-A) used for the modified filler B, jER YX4000H was used. Except for this, production and evaluation were performed in the same manner as in Example 2.

[Example 4]
As a silane coupling agent used for the modified fillers A to C, bisphenol A, 2-ethyl-4-methyl-imidazole is used as an additive instead of the compound represented by the formula (2-A) used for the modified filler B S510 was used. At this time, pure water was used as a solvent when the modified filler A was prepared, and the drying temperature of the mixture was set to 60 degrees. Furthermore, the mixing temperature using the two rolls when the modified filler B was prepared was set to 160 ° C. Except for this, production and evaluation were performed in the same manner as in Example 2.

[Comparative Example 1]
A compression molding machine (Imoto Seisakusho Co., Ltd.) set at 150 ° C. by mixing 0.56 g of modified filler B and 0.14 g of modified filler A and sandwiching the resulting mixture in a stainless steel plate using a metal frame so as not to be oxidized. Pre-curing was performed by pressurizing to 20 MPa using IMC-19EC) and continuing the heating state for 15 minutes. That is, when the mixture spreads between the stainless steel plates, since BN is plate-like particles, the particles and the stainless steel plates were oriented in parallel. The amount of the metal frame and the sample was adjusted so that the thickness of the sample was about 500 μm. Further, curing was carried out using a vacuum oven at 80 ° C. for 3 hours and at 200 ° C. for 14 hours. Thereafter, evaluation was performed in the same manner as in Example 1.

[Comparative Example 2]
As the modified filler C aluminum nitride, AlN whisker manufactured by U-Map Co., Ltd., which is not treated with a silane coupling agent, was used. Except this, it produced and evaluated similarly to Example 1. FIG.

[Comparative Example 3]
An AlN whisker manufactured by U-Map Co., Ltd., which is not treated with a silane coupling agent as aluminum nitride of the modified filler C, was cut into a length of about 3 mm and used. Except this, it produced and evaluated similarly to Example 1. FIG.

[Comparative Example 4]
As the modified filler C aluminum nitride, a crushed AlN whisker manufactured by U-Map Co., Ltd., which was not treated with a silane coupling agent was used. Except this, it produced and evaluated similarly to Example 1. FIG.

  The results of the compositions of Examples and Comparative Examples, the treatment method, the thermal conductivity in the vertical direction, and the thermal expansion coefficient are shown in Table 1 and FIGS.

  As shown in Table 1 above, when using the modified filler C in which the aluminum nitride whisker is the third inorganic filler and the silane coupling agent manufactured by JNC is the third silane coupling agent, boron nitride, polymerizable Since the heat radiation member having a high filling property was obtained in a state where the liquid crystal, the silane coupling agent and the aluminum nitride whisker were directly bonded, the thermal conductivity in the vertical direction was high. The thermal conductivity was particularly good when crushed particulate aluminum nitride whiskers were used.

DESCRIPTION OF SYMBOLS 1 1st inorganic filler 2 2nd inorganic filler 3 3rd inorganic filler 11 1st coupling agent 12 2nd coupling agent 13 3rd coupling agent 22 Bifunctional or more polymeric compound

Claims (13)

A first coupling agent;
A thermally conductive first inorganic filler bonded to one end of the first coupling agent;
A second coupling agent;
A thermally conductive second inorganic filler bonded to one end of the second coupling agent;
A bifunctional or higher functional polymerizable compound bonded to the other end of the second coupling agent;
A third coupling agent;
A thermally conductive third inorganic filler bonded to one end of the third coupling agent;
The first coupling agent and the polymerizable compound each have a group capable of binding to each other;
The third coupling agent and the polymerizable compound each have a group capable of binding to each other;
The third inorganic filler is a nitride whisker.
Composition for heat dissipation member. A first coupling agent;
A thermally conductive first inorganic filler bonded to one end of the first coupling agent;
A second coupling agent;
A thermally conductive second inorganic filler bonded to one end of the second coupling agent;
A third coupling agent;
A thermally conductive third inorganic filler bonded to one end of the third coupling agent;
The first coupling agent and the second coupling agent each have a group capable of binding to each other,
The third coupling agent and the second coupling agent each have a group capable of binding to each other,
The third inorganic filler is a nitride whisker.
Composition for heat dissipation member. The average particle diameter of the first inorganic filler and the second inorganic filler is 0.1 to 500 μm,
The nitride whiskers are acicular, fibrous, or particulate.
The composition for heat radiating members according to claim 1 or 2. 0.1 to 10 parts by mass of the third inorganic filler is included with respect to 100 parts by mass of the total amount of the first inorganic filler and the second inorganic filler.
The composition for heat radiating members of any one of Claims 1-3. The first inorganic filler and the second inorganic filler are each independently at least selected from boron nitride, aluminum nitride, carbon nitride boron, boron carbide, graphite, carbon fiber, carbon nanotube, alumina, and cordierite. One,
The composition for heat radiating members of any one of Claims 1-4. The third inorganic filler is at least one selected from aluminum nitride whiskers and boron nitride whiskers.
The composition for heat radiating members of any one of Claims 1-5. Further comprising an organic compound, a polymer compound, or an inorganic compound not bonded to the first inorganic filler, the second inorganic filler, and the third inorganic filler,
The composition for heat radiating members of any one of Claims 1-6. The polymerizable compound before binding to the coupling agent is at least one of a bifunctional or higher-polymerizable non-liquid crystal compound represented by the following formula (1).
The composition for heat radiating members according to any one of claims 1 and 3-7.

R ^a —R ⁶ —O— (Rx) _n —O—R ¹¹ —R ^a (1)

[In the above formula (1),
Each R ^a is independently any of the following formulas (1-1) to (1-2), amino, vinyl, carboxylic anhydride residues, or any polymerizable group containing these structures;
Rx is any one of the following formulas (1-3) to (1-6);
n is an integer from 1 to 3;
R ⁶ and R ¹¹ are each independently a single bond or alkylene having 1 to 20 carbon atoms. ]

[In the formulas (1-1) to (1-2), R ^b is independently hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbon atoms, and q is 0 or 1. . ]

[In formulas (1-4) to (1-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms. ] The first coupling agent, the second coupling agent, and the third coupling agent are silane coupling agents represented by the following formula (6), respectively.
The composition for heat radiating members of Claim 8.

_{^{(R 1 -O) j -Si (}} R 5) 3-j - (R 2) k - (R 3) m - (R 4) n -Ry (6)

[In the above formula (6),
R ¹ is H-, or CH _3- (CH ₂ ) _{0 -4-} ;
R ² is — (CH ₂ ) _0-3- O—;
R ³ is 1,3-phenylene, 1,4-phenylene, naphthalene-2,6-diyl, or naphthalene-2,7-diyl;
R ⁴ _{is, - (NH) 0~1 - (} CH 2) 0~3 - a and;
R ⁵ is H— or CH ₃ — (CH ₂ ) _0-7 —;
Ry is oxiranyl, oxetanyl, amino, vinyl, carboxylic anhydride residue, or any polymerizable group containing these structures;
j is an integer from 0 to 3;
k is an integer from 0 to 1;
m is an integer from 0 to 1;
n is an integer from 0 to 1;
Formula (6) includes at least one of R ³ and R ⁴ . ] The polymerizable compound before being bonded to the coupling agent is at least one of a bifunctional or higher functional polymerizable liquid crystal compound represented by the following formula (2).
The composition for heat radiating members according to any one of claims 1 and 3-7.

Ra-Z- (AZ) m-Ra (2)

[In the formula (2),
Each Ra is independently a group capable of binding to the other end of the first coupling agent, the second coupling agent, or the third coupling agent;
A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, arbitrary —CH ₂ — may be replaced with —O—, optional —CH═ may be replaced with —N═, and optional hydrogen is halogen, carbon number 1 Or an alkyl halide having 1 to 10 carbon atoms or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH═CH—, or —C≡C—;
Each Z is independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —CH ₂ — represents —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═N—, -N = CH-, -N = N-, -N (O) = N-, or -C≡C-, and any hydrogen may be replaced by halogen;
m is an integer of 1-6. ] The polymerizable compound before binding with the coupling agent is at least one polymerizable non-liquid crystal compound having a bifunctional or higher functional hydroxy group represented by the following formula (3) or (4).
The composition for heat radiating members according to any one of claims 1 and 3-7.

[In the above formula (3),
R ¹ and R ² are each independently hydrogen, halogen, or alkyl having 1 to 3 carbon atoms;
m is an integer of 2 to 4, n is an integer of 1 to 3, p is an integer of 2 to 4, q is an integer of 1 to 3, m + n = 5, and p + q = 5 Yes;
A represents a single bond, alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′-(9-fluorenylidene) diphenylene, adamantanediyl, or biadamantanediyl And
In the alkylene having 1 to 10 carbon atoms, arbitrary hydrogen may be replaced with —CH ₃ ;
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, In bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′-(9-fluorenylidene) diphenylene, adamantanediyl or biadamantanediyl, any —CH ₂ — is —O—. Any -CH = may be replaced by -N =, and any hydrogen is replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons May be
In the alkyl substituted with any hydrogen, any —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, any —CH ₂ — may be replaced with —O—, —S—, —CO—, —COO—, or —OCO—, and any hydrogen may be replaced with a halogen. . ]
[In the above formula (4),
x is an integer greater than or equal to 2;
Ring B is benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, 9,9-diphenylfluorene, adamantane, or biadamantane;
In Ring B, any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any hydrogen may be a halogen, a carbon number of 1 to 3 alkyl, or an alkyl halide having 1 to 3 carbon atoms,
In the alkyl having 1 to 3 carbon atoms or the alkyl halide having 1 to 3 carbon atoms in the ring B, arbitrary —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. May be. ] It is a cured product of the composition for heat dissipation member according to any one of claims 1 to 11.
Heat dissipation member. A heat dissipating member according to claim 12;
An electronic device having a heat generating part;
Arranged in the electronic device so that the heat dissipation member is in contact with the heat generating part,
Electronics.

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