JPWO2018181838A1 - Composition for heat dissipating member, heat dissipating member, electronic device, method for manufacturing heat dissipating member - Google Patents

Abstract

The present invention is a composition having high thermal conductivity, capable of controlling the coefficient of thermal expansion, and having high heat resistance and capable of forming a heat dissipation member. The heat-dissipating member composition of the present application includes a thermally conductive first inorganic filler 1 bonded to one end of a first coupling agent; and a thermally conductive second inorganic filler 1 bonded to one end of a second coupling agent. A second inorganic filler in which a bifunctional or higher functional polymerizable compound 22 is further bonded to the other end of the second coupling agent. The bifunctional or higher functional polymerizable compound is a non-liquid crystalline compound, and at least one of the functional groups of the polymerizable compound can be bonded to the other end of the first coupling agent.

Description

  The present invention relates to a composition for a heat dissipation member. In particular, the present invention relates to a composition for a heat dissipating member capable of forming a heat dissipating member capable of efficiently dissipating heat generated inside an electronic device by conducting and transmitting the heat and controlling the coefficient of thermal expansion.

  2. Description of the Related Art In recent years, in a semiconductor element for power control in a hybrid vehicle or an electric vehicle, a CPU for a high-speed computer, and the like, it is desired that the package material has high thermal conductivity so that the temperature of the internal semiconductor does not become too high. That is, the ability to effectively release the heat generated from the semiconductor chip to the outside has become important. In addition, a rise in operating temperature causes thermal distortion due to a difference in coefficient of thermal expansion between materials used in the package, resulting in a problem of shortening of life due to peeling of wiring and the like.

  As a method of solving such a heat radiation problem, a method of bringing a heat conductive material (a heat radiation member) into contact with a heat generating portion to guide heat to the outside and dissipate the heat is used. Patent Literature 1 discloses a heat dissipating member in which an organic material and an inorganic material are combined, wherein the inorganic material is connected with a coupling agent and a polymerizable liquid crystal compound (paragraph 0007, FIG. 1). 2). By connecting the coupling agent and the polymerizable liquid crystal compound, the thermal conductivity between the inorganic materials can be extremely increased.

International Publication No. WO 2016/031888

However, liquid crystal compounds have many reactive sites and are susceptible to heat.
Therefore, an object of the present invention is to provide a composition and a heat dissipating member having high thermal conductivity, capable of controlling the coefficient of thermal expansion, and further having high heat resistance and capable of forming a heat dissipating member.

  The present inventors have found that when a composition having a specific structure among a polymerizable compound and a coupling agent is used in a composition for a heat dissipation member, the composition has high thermal conductivity, can control the coefficient of thermal expansion, and further improves heat resistance. The inventors have found that the present invention can be performed, and completed the present invention.

式（２−１）〜（２−２）中、Ｒ^ｂは、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（２−４）〜（２−６）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。
「一端」および「他端」とは、分子の形状の縁または端であればよく、分子の長辺の両端であってもなくてもよい。
このように構成すると、無機フィラー同士をカップリング剤および重合性化合物を介して直接結合させて放熱部材を形成することができる。そのため、熱伝導の主な要素であるフォノンを直接伝播することができ、硬化後の放熱部材は水平方向だけでなく厚み方向にも極めて高い熱伝導性を有することができる。さらに、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。For example, as shown in FIG. 2, the heat-radiating member composition according to the first embodiment of the present invention includes a heat-conductive first inorganic filler 1 bonded to one end of a first coupling agent 11; A second inorganic filler 2 bonded to one end of the coupling agent 12, wherein a bifunctional or higher functional polymerizable compound 22 is further bonded to the other end of the second coupling agent 12. And the second coupling agent 12 has a polymerizable compound represented by the following formula (1-1) bonded as the bifunctional or higher polymerizable compound 22; The polymerizable compound 22 is a non-liquid crystalline compound, and at least one of the functional groups of the polymerizable compound 22 can be bonded to the other end of the first coupling agent 11.
_{^{R a -R 6 -O- (Rx)}} n -O-R 11 -R a (1-1)
In the above formula (1-1),
^Ra is each of the following formulas (2-1) to (2-2), amino, vinyl, a carboxylic anhydride residue, or any polymerizable group containing these structures;
Rx is any of the following formulas (2-3) to (2-6);
n is an integer from 1 to 3;
R ⁶ and R ¹¹ are each independently a single bond or an alkylene having 1 to 20 carbon atoms.

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

In the formulas (2-4) to (2-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms.
“One end” and “the other end” may be edges or edges of the shape of the molecule, and may or may not be both ends of the long side of the molecule.
With this configuration, the inorganic filler can be directly bonded to each other via the coupling agent and the polymerizable compound to form a heat dissipation member. Therefore, phonon, which is a main component of heat conduction, can be directly propagated, and the heat radiation member after curing can have extremely high thermal conductivity not only in the horizontal direction but also in the thickness direction. Furthermore, since the structure of the polymerizable compound has few reaction sites and is hardly affected by heat, the heat dissipation member can have high heat resistance.

The composition for a heat radiation member according to the second aspect of the present invention is the composition for a heat radiation member according to the first aspect of the present invention, wherein the first inorganic filler and the second inorganic filler are the It is a composition in which a silane coupling agent represented by the following formula (3-1) is bonded as the first coupling agent and the second coupling agent.
^{_{(R 1 -O) j -Si (}} R 5) 3-j - (R 2) k - (R 3) k - (R 4) k -Ry
(3-1)
In the above formula (3-1),
R ¹ is H—, or CH ₃ — (CH ₂ ) ₀ — ₄ —;
R ² _is, - _{(CH 2) 0~3} -O- and is;
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} - a and;
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;
Formula (3-1) includes at least one of R ³ and R ⁴ .
With such a configuration, the structure of the coupling agent has few reaction sites and is hardly affected by heat, so that the heat dissipation member can have high heat resistance.

The heat-dissipating member composition according to the third aspect of the present invention is the heat-dissipating member composition according to the first or second aspect of the present invention, wherein the first inorganic filler and the second inorganic filler are used. The fillers are boron nitride, boron carbide, boron carbon nitride, graphite, carbon fiber, carbon nanotube, graphene, alumina, aluminum nitride, silica, silicon nitride, silicon carbide, zinc oxide, magnesium oxide, magnesium hydroxide, cordier, respectively. It is at least one selected from light or an iron oxide-based material.
With such a configuration, the inorganic filler has a high thermal conductivity, a positive or very small thermal expansion coefficient, or a negative thermal expansion coefficient. can get.

The composition for a heat dissipation member according to a fourth aspect of the present invention is the composition for a heat dissipation member according to any one of the first to third aspects of the present invention, wherein the first inorganic filler is used. And a third inorganic filler having a coefficient of thermal expansion different from that of the second inorganic filler.
With this configuration, when the first inorganic filler and the second inorganic filler have different coefficients of thermal expansion, when they are compounded, the coefficient of thermal expansion of the compounded heat dissipation member composition is Is an intermediate value in the case of compounding with only the fillers. However, if there are many gaps between the fillers as they are, not only the thermal conductivity does not increase, but also the electric insulation is reduced due to the intrusion of moisture into the gaps. Therefore, by adding a third inorganic filler having a high thermal conductivity and a smaller particle size than the first and second inorganic fillers, the gap between the first and second inorganic fillers is filled, and the stability of the material is improved. Make it higher. Furthermore, by adding a third inorganic filler having a higher thermal conductivity than when only the first and second inorganic fillers are used, it is possible to increase the thermal conductivity of the heat radiation member. There is no restriction on the inorganic filler used for the third inorganic filler, but if high insulation is required, boron nitride, aluminum nitride, silicon carbide, silicon nitride, or diamond or carbon if high insulation is not required. It is desirable that the material has high thermal conductivity, such as nanotubes, graphene, and metal powder.

The composition for a heat radiation member according to a fifth aspect of the present invention is the composition for a heat radiation member according to any one of the first to fourth aspects of the present invention, wherein the first inorganic filler is used. And an organic compound or a polymer compound not bound to the second inorganic filler.
With this configuration, in the heat dissipation member cured by connecting the first and second inorganic fillers, as the particle diameter of the filler is increased in order to improve the thermal conductivity, the porosity increases accordingly. In such a case, the voids can be filled with a non-bonded compound, and the thermal conductivity and the water vapor blocking performance can be improved.

A heat dissipation member according to a sixth aspect of the present invention is a heat dissipation member obtained by curing the composition for a heat dissipation member according to any one of the first to fifth aspects of the present invention.
With this configuration, the heat dissipation member has a bond between the inorganic fillers, and can have extremely high thermal conductivity and heat resistance.

An electronic apparatus according to a seventh aspect of the present invention includes the heat radiating member according to the sixth aspect of the present invention; and an electronic device having a heat generating portion, wherein the heat radiating member is in contact with the heat generating portion. Is disposed on the electronic device.
With this configuration, the heat generated in the electronic device can be efficiently conducted by the heat dissipating member having high thermal conductivity and high heat resistance. Further, by keeping the coefficient of thermal expansion in the plane direction close to the coefficient of thermal expansion of a semiconductor element such as copper wiring, silicon, or silicon nitride attached to the heat radiating member, peeling due to a heat cycle can be suppressed.

式（２−１）〜（２−２）中、Ｒ^ｂは、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（２−４）〜（２−６）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、無機フィラー間をカップリング剤および重合性化合物を介して結合した無機フィラーを含む放熱部材であって、高耐熱性の放熱部材を製造することができる。A method for manufacturing a heat radiation member according to an eighth aspect of the present invention includes, as shown in FIG. 2, for example, a step of bonding the first inorganic filler 1 having thermal conductivity to one end of the first coupling agent 11; Bonding the thermally conductive second inorganic filler 2 to one end of the second coupling agent 12; and bonding the other end of the second coupling agent 12 to a bifunctional or higher functional polymerizable compound 22. And bonding the other end of the first coupling agent 11 to the bifunctional or higher functional polymerizable compound 11. The bifunctional or higher functional polymerizable compound 22 is represented by the following formula (1) -1), wherein the polymerizable compound is a non-liquid crystalline compound.
_{^{R a -R 6 -O- (Rx)}} n -O-R 11 -R a (1-1)
In the above formula (1-1),
^Ra is each of the following formulas (2-1) to (2-2), amino, vinyl, a carboxylic anhydride residue, or any polymerizable group containing these structures;
Rx is any of the following formulas (2-3) to (2-6);
n is an integer from 1 to 3;
R ⁶ and R ¹¹ are each independently a single bond or an alkylene having 1 to 20 carbon atoms.

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

In the formulas (2-4) to (2-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms.
With this configuration, it is possible to manufacture a heat-dissipating member including an inorganic filler in which inorganic fillers are bonded via a coupling agent and a polymerizable compound, and having high heat resistance.

  The heat dissipating member formed from the composition for a heat dissipating member of the present invention has extremely high thermal conductivity, controllability of the coefficient of thermal expansion, and high heat resistance. In addition, it has excellent properties such as chemical stability, hardness, and mechanical strength. The heat dissipating member is suitable for, for example, a heat dissipating substrate, a heat dissipating plate (a planar heat sink), a heat dissipating sheet, a heat dissipating coating film, and a heat dissipating adhesive.

FIG. 4 is a conceptual diagram illustrating a bond between inorganic fillers in a heat dissipation member of the present application, using boron nitride as an example. FIG. 4 is a conceptual diagram showing that the other end of the coupling agent 11 bonded to the first inorganic filler 1 is bonded to the polymerizable compound 22 of the second inorganic filler 2 by curing of the heat dissipation member composition. It is a conceptual diagram which shows the manufacturing process of the filler A, the filler B, and a heat dissipation member.

  This application is based on Japanese Patent Application No. 2017-072255 filed on March 31, 2017 in Japan, the contents of which are incorporated in and form a part of the present application. The present invention will become more fully understood from the detailed description below. Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. However, the detailed description and specific examples are preferred embodiments of the present invention, and are described for illustrative purposes only. From this detailed description, various changes and modifications will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Applicant does not intend to publish any of the described embodiments to the public, and any modifications or alternatives, which may not be literally within the scope of the claims, may be made under the doctrine of equivalents. Of the present invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each of the drawings, the same or corresponding portions are denoted by the same or similar reference numerals, and duplicate description will be omitted. Further, the present invention is not limited to the following embodiments.

The usage of terms in this specification is 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.
A “polymerizable group” is a group that participates in a polymerization reaction.

"Arbitrary -CH ₂ in the alkyl - is, -O- may be replaced by such" or "arbitrary _-CH 2 CH ₂ - is replaced may be like -CH = CH-" phrase, such as The meaning is shown in the following example. For _example, C 4 _{H 9} - optional -CH at ₂ -, -O- or Examples of the group is replaced by _{-CH = CH-, C 3 H 7} O-, CH 3 -O- (CH 2) 2 —, CH ₃ —O—CH ₂ —O— and the like. Similarly _C 5 _{H 11} - Any of the _-CH 2 CH ₂ -. Examples of the group which is replaced by _{-CH = CH-, H 2 C =} CH- (CH 2) 3 -, CH 3 -CH = CH - _{(CH 2) 2} -, etc., further optional -CH ₂ - as has been replaced by -O- _{groups, CH 3 -CH = CH-CH} 2 -O- , and the like. Thus, the term "arbitrary" means "at least one selected indiscriminately." 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 is better 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 carbons, or alkyl halide having 1 to 10 carbons” with respect to the ring A is, for example, 2 'of 1,4-phenylene , 3, 5 and 6 means that at least one of the hydrogens is replaced by a substituent such as fluorine or a methyl group, and that the substituent is "halogenated alkyl having 1 to 10 carbon atoms" Examples of the above include examples such as a 2-fluoroethyl group and a 3-fluoro-5-chlorohexyl group.

“Compound (1-2)” means a liquid crystal compound represented by the following formula (1-2), and at least one compound represented by the following formula (1-2). Sometimes. “Composition for heat dissipation member” means a composition containing at least one compound selected from the above compound (1-2) and other polymerizable compounds. When one compound (1-2) has a plurality of A's, any two A's may be the same or different. When a plurality of compounds (1-2) have A, any two A may be the same or different. This rule also applies to other symbols, groups, etc., such as ^Ra and Z.

[Composition for heat dissipation member]
The composition for a heat radiating member of the present application is a composition that forms a heat radiating member by curing, whereby inorganic fillers are bonded to each other via a coupling agent and a bifunctional or more polymerizable compound. FIG. 1 shows an example in which boron nitride is used as an inorganic filler. When boron nitride (h-BN) is treated with a coupling agent, in the case of boron nitride, the coupling agent bonds only around the periphery of the particle because there is no reactive group on the plane of the particle. Boron nitride treated with a coupling agent can form a bond with a polymerizable compound. Therefore, as shown in FIG. 2, the other end of the coupling agent 11 of the boron nitride 1 subjected to the coupling treatment and the other end of the polymerizable compound 22 of the boron nitride 2 which has been subjected to the coupling treatment and modified with the polymerizable compound 22. The boron nitride can be bonded to each other as shown in FIG.
In this way, by bonding the inorganic filler to each other via the coupling agent and the polymerizable compound, phonons can be directly propagated, so that the heat radiation member after curing has extremely high thermal conductivity, It becomes possible to produce an organic-inorganic composite material that 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 is, for example, as shown in FIGS. 1 and 2, a first thermally conductive first agent coupled to one end of a plurality of first coupling agents 1. An inorganic filler 11; a thermally conductive second inorganic filler 2 bonded to one end of a plurality of second coupling agents 12; And a second inorganic filler to which the polymerizable compound 22 is bonded.
As shown in FIG. 2, when the composition for a heat radiating member is cured, the other end of the coupling agent 11 bonded to the first inorganic filler 1 is bonded to the polymerizable compound 22 of the second inorganic filler 2. In this way, a bond between the inorganic fillers is formed.

式（２−１）〜（２−２）中、Ｒ^ｂは、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（２−４）〜（２−６）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。[Bifunctional or higher polymerizable compound]
The bifunctional or higher functional polymerizable compound may be a non-liquid crystalline compound. The bifunctional or higher functional polymerizable compound has a functional group capable of forming a bond with a coupling agent.
Examples of the bifunctional or higher functional polymerizable compound include a polymerizable compound represented by the following formula (1-1).
_{^{R a -R 6 -O- (Rx)}} n -O-R 11 -R a (1-1)
In the above formula (1-1),
^Ra is each of the following formulas (2-1) to (2-2), amino, vinyl, a carboxylic anhydride residue, 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 (2-3) to (2-6). ', Biphenyl-3,3';
n is an integer from 1 to 3;
R ⁶ and R ¹¹ are each independently a single bond or an alkylene having 1 to 20 carbon atoms.

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

In the formulas (2-4) to (2-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms.

Incidentally, R ^a is independently, may be a first end of functional group and a second functional group capable of binding a functional group at the other end of the coupling agent of the coupling agent. For example, in addition to the polymerizable groups represented by the above formulas (2-1) to (2-2), cyclohexene oxide, phthalic anhydride, or succinic anhydride can be given, but not limited thereto.
Examples of combinations of functional groups that form a bond between ^Ra and a coupling agent include, for example, combinations of oxiranyl and amino, vinyl and methacryloxy, carboxy or carboxylic anhydride residues and amines, imidazole and oxiranyl, and the like. But not limited to these. Any combination of functional groups capable of forming a bond between the polymerizable compound and the coupling agent may be used. Combinations with high heat resistance are more preferred.

  The polymerizable compound represented by the formula (1-1) has few reaction sites in its structure and is hardly affected by heat. On the other hand, the structure was found to be excellent in phonon propagation. Therefore, the heat dissipating member formed from the composition for a heat dissipating member can have high heat resistance as well as high thermal conductivity.

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 (1-2).
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 (1-2) tends to be uniform when mixed with another liquid crystal compound, a polymerizable compound, or the like.
_{^{R a -Z- (A-Z)}} m -R a (1-2)

By appropriately selecting the terminal group ^Ra , the ring structure A, and the bonding group Z of the compound (1-2), physical properties such as a liquid crystal phase expression region can be arbitrarily adjusted. The effects of the type of the terminal group R ^a , the ring structure A and the bonding group Z on the physical properties of the compound (1-2), and preferable examples thereof, will be described below.

・ Terminal group R ^a
Terminal groups ^{R a} has the same meaning as ^{R a} as defined by the above formula (1-1).

・ Ring structure A
When at least one ring in the ring structure A of the compound (1-2) is 1,4-phenylene, the orientational order parameter and the magnetization 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.

  Preferred 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-dimethylfluorene-2,7- Yl, 9-ethyl-2,7-diyl, 9-fluoro-2,7-diyl, 9,9-like 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.

  More preferred 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.

.Binding group Z
Bonding group Z of the compound (1-2) is a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF- or - _{(CH 2) 4} - when it, in particular a single _{bond, - (CH 2) 2 -} , - CF 2 O -, - OCF 2 -, - CH = CH- or - In the case of (CH ₂ ) ₄ —, the viscosity decreases. 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. When the bonding group Z is an alkyl having about 4 to 10 carbon atoms, the melting point decreases.

Preferred Z, 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.

More preferred Z, 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. Particularly preferred Z, a single _{bond, - (CH 2) 2 -} , - COO- or -OCO-.

  The more the compound (1-2) has more rings, the more difficult it is to soften at a higher temperature, so it is preferable as a heat-radiating material. However, if the softening temperature is higher than the polymerization temperature, molding becomes difficult. It is preferable to take In the present specification, a 6-membered ring or a fused ring containing the 6-membered ring is basically 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 (1-2) may be optically active or optically inactive. When the compound (1-2) is optically active, the compound (1-2) may have an asymmetric carbon or may have 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. When the compound has an asymmetric carbon, the compound (1-2) has good compatibility. When the compound (1-2) has axial asymmetry, the twist inducing force is large. Further, the light-irradiating property may be any.
As described above, by appropriately selecting the type of the terminal group R ^a , the ring structure A and the bonding group Z, and the number of rings, a compound having desired physical properties can be obtained.

-Compound (1-2)
Compound (1-2) can also be represented by the following formula (1-a) or (1-b).
P-Y- (AZ) _m- ^Ra (1-a)
P-Y- (AZ) _m- Y-P (1-b)

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

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

  Preferred examples of the compound (1-2) include the following compounds (a-1) to (a-10), (b-1) to (b-16), and (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) No. * In the formula represents an asymmetric carbon.

In the above chemical formulas (a-1) to (g-20), R ^a , P and Y are as defined in the above formulas (1-a) and (1-b).
Z ¹ are 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 is O-. Incidentally, a plurality of Z ¹ may be the same or different.

Z ² is each independently — (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 is O-.

Z ³ is each independently 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 a plurality of Z ³ may be the same or different. a is an integer of 1 to 20.

  X is a substituent of 1,4-phenylene and fluorene-2,7-diyl in which arbitrary hydrogen may be replaced by halogen, alkyl or alkyl fluoride, and represents halogen, alkyl or alkyl fluoride.

A more preferred embodiment of the compound (1-2) will be described. More preferred compound (1-2) can be represented by the following formula (1-c) or (1-d).
P ¹ -Y- (AZ) _m -R ^a (1-c)
P ¹ -Y- (AZ) _m -YP ¹ (1-d)
In the above ^{formula, A, Y, Z, R} a and m are as previously defined, ^{P 1} represents a polymerizable group represented by the following formula (2-1) to (2-2). If the above formula (1-d), two ^{P 1} represents the same polymerizable group (2-1) to (2-2), two Y may represent the same group, the two Y are symmetrical Combine so that

  More preferred specific examples of the compound (1-2) are shown below.

-Method for synthesizing compounds (1-1) and (1-2) The compounds (1-1) and (1-2) can be synthesized by combining known methods in synthetic organic chemistry. Methods for introducing the desired terminal groups, ring structures and linking groups into the starting materials are described, for example, in Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John. Wily & Sons, Inc.), Organic Reactions, John Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Laboratory Chemistry Course (Maruzen) It is described in. Moreover, you may refer to Unexamined-Japanese-Patent No. 2006-265527.

The bifunctional or higher functional polymerizable compound (hereinafter, may be simply referred to as “polymerizable compound”) may be a polymerizable compound other than the polymerizable compounds represented by the above formulas (1-1) and (1-2). . For example, among the diglycidyl ether of polyether, the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, the diglycidyl ether of biphenol, and the compound of formula (1-2), linearity is insufficient and liquid crystallinity is exhibited. And the like.
The polymerizable compound can be synthesized by combining known methods in synthetic organic chemistry.

The polymerizable compound used in the present invention preferably has a bifunctional or more functional group in order to form a bond with a coupling agent, and includes a case of a trifunctional or more or a tetrafunctional or more. Further, a compound having a functional group at both ends of the long side of the polymerizable compound is preferable because a linear bond can be formed.
If the surface modification with the polymerizable compound or the like is too small, the strength of the resin is low because the number of molecules binding between the fillers is too small, and if the surface modification is too large, the properties of the resin such as a glass transition temperature are exhibited. Therefore, it is desirable to appropriately adjust the amount of surface modification depending on the required characteristics.

[Inorganic filler]
Examples of the first inorganic filler and the second inorganic filler include a nitride, a carbide, a carbon material, a metal oxide, and a silicate mineral. The first inorganic filler and the second inorganic filler may be the same or different.
Specifically, the first inorganic filler and the second inorganic filler include, as inorganic fillers having high thermal conductivity and a very small or negative coefficient of thermal expansion, boron nitride, boron carbide, boron carbon nitride, graphite, Examples include carbon fibers and carbon nanotubes. Alternatively, alumina, silica, magnesium oxide, zinc oxide, iron oxide, ferrite, mullite, cordierite, silicon nitride, and silicon carbide can be given.
Alternatively, the following inorganic filler having a high thermal conductivity and a positive coefficient of thermal expansion may be used as one of the first and second inorganic fillers.

  As the third inorganic filler, an inorganic filler having a high thermal conductivity, a smaller size than the first and second inorganic fillers, and a different thermal expansion coefficient from the first and second inorganic fillers is used. preferable. For example, alumina, silica, boron nitride, boron carbide, silicon carbide, aluminum nitride, silicon nitride, diamond, carbon nanotube, graphite, graphene, silicon, beryllia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, oxide Titanium, 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 , Tungsten, molybdenum, stainless steel, and other inorganic fillers and metal fillers. The third inorganic filler may be unmodified, modified with a coupling agent, or modified with a coupling agent and a polymerizable compound.

  It is desirable that the structure of the polymerizable compound has a shape and a length that enable efficient direct bonding between these inorganic fillers. The type, shape, size, addition amount, and the like of the inorganic filler can be appropriately selected depending on the purpose. In the case where the obtained heat radiating member requires insulation, a conductive inorganic filler 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 fibrous shape, a rod shape, and a cylindrical shape.

  The inorganic filler is preferably boron nitride, aluminum nitride, silicon nitride, silicon carbide, graphite, carbon fiber, or carbon nanotube. Particularly, 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 a high insulating property. 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 average particle size of the inorganic filler is preferably from 0.1 to 200 μm. More preferably, it is 1 to 100 μm. 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 a particle size distribution measurement by a laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle diameter by the wet method using the analysis based on the Franhofer diffraction theory and Mie's scattering theory, the diameter where the larger side and the smaller side are equal (based on volume). Is the median diameter.
The ratio of the inorganic filler to the coupling agent and the polymerizable compound depends on the amount of the coupling agent to be combined with the inorganic filler used. The compound (for example, boron nitride) used as the first and second inorganic fillers has no reactive group on the surface as described above, and has a reactive group only on the side surface. It is preferable to couple as many coupling agents as possible to the small number of reactive groups and to bind the same number or a little more organic compounds as the number of the reactive groups. The reaction amount of the coupling agent to the inorganic filler mainly changes depending on the size of the inorganic filler and the reactivity of the coupling agent used. For example, as the size of the inorganic filler increases, the area ratio of the side surface of the inorganic filler decreases, so that the amount of modification is small. It is desirable to react as many coupling agents as possible, but it is preferable to balance the particles since the thermal conductivity of the product decreases as the particles become smaller.
The volume ratio of the coupling agent and the polymerizable compound to the inorganic component in the heat dissipation member is preferably in the range of 5:95 to 30:70, and more preferably 10:90 to 25:75. desirable. The inorganic component is an inorganic raw material before a silane coupling agent treatment or the like is performed.

[Coupling agent]
The coupling agent to be bonded to the inorganic filler has a functional group that can be bonded to the functional group of the polymerizable compound having two or more functions. Examples of the coupling agent include a silane coupling agent represented by the following formula (3-1).
^{_{(R 1 -O) j -Si (}} R 5) 3-j - (R 2) k - (R 3) k - (R 4) k -Ry
(3-1)
In the above formula (3-1),
R ¹ is H—, or CH ₃ — (CH ₂ ) ₀ — ₄ —;
R ² _is, - _{(CH 2) 0~3} -O- and is;
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} - a and;
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;
Formula (3-1) includes at least one of R ³ and R ⁴ .

When the functional group of the polymerizable compound having two or more functional groups is oxiranyl, an acid anhydride residue, or the like, it is preferable to react with such a functional group. Therefore, those having an amine-based reactive group at the terminal are preferable. For example, a product manufactured by JNC Co., Ltd. includes Sila Ace (registered trademark) S310, S320, S330, S360, and a product manufactured by Shin-Etsu Chemical Co., Ltd. include KBM903 and KBE903.
When the terminal of the bifunctional or higher functional polymerizable compound is an amine, a coupling agent having oxiranyl or the like at the terminal is preferable. For example, a product manufactured by JNC Co., Ltd. includes Sila Ace (registered trademark) S510 and S530.
Examples of the combination of the functional group that forms the bond between the coupling agent and the polymerizable compound include, for example, a combination of oxiranyl and amino, between vinyl, between methacryloxy, between a carboxy or carboxylic anhydride residue and an amine, a combination between imidazole and oxiranyl, and the like. Examples include, but are not limited to: Any combination of functional groups capable of forming a bond between the coupling agent and the polymerizable compound may be used. Combinations with high heat resistance are more preferred.
Modification of the inorganic filler with a coupling agent is preferable because the larger the number, the more the bonding. The first coupling agent and the second coupling agent may be the same or different.

[Other components]
The composition for a heat radiating member may further contain an organic compound (for example, a polymerizable compound or a polymer compound) that is not bonded to the first inorganic filler and the second inorganic filler, that is, does not contribute to the bonding. , A polymerization initiator and a solvent.

[Polymerizable compound not bonded]
The composition for a heat radiation member may include a polymerizable compound that is not bonded to an inorganic filler (in this case, the composition is not necessarily bifunctional or more). As such a polymerizable compound, a compound which does not hinder the thermosetting of the inorganic filler and does not evaporate or bleed out by heating is preferable. This polymerizable compound is classified into a compound having no liquid crystal and a compound having liquid crystal. Examples of the polymerizable compound having no liquid crystallinity include a vinyl derivative, a styrene derivative, a (meth) acrylic acid derivative, a sorbic acid derivative, a fumaric acid derivative, and an itaconic acid derivative. As for the content, it is desirable to first prepare a composition for a heat dissipation member that does not contain an unbonded polymerizable compound, measure the porosity, and add an amount of the polymerizable compound that can fill the void.

[Unbound polymer compound]
The composition for a heat dissipation member may include a polymer compound that is not bonded to an inorganic filler. As such a high molecular compound, a compound which does not decrease the film forming property and the mechanical strength is preferable. The polymer compound may be any polymer compound that does not react with the inorganic filler, the coupling agent, and the polymerizable compound.For example, when the polymerizable compound is oxiranyl and the silane coupling agent has an amino, a polyolefin resin , Polyvinyl resins, silicone resins, waxes and the like. As for the content, it is desirable to first prepare a composition for a heat dissipation member that does not contain a polymer compound that is not bonded, measure the porosity, and add an amount of the polymer compound that can fill the void.

[Non-polymerizable liquid crystal compound]
The composition for a heat dissipation member may include a liquid crystal compound having no polymerizable group as a constituent element. Examples of such non-polymerizable liquid crystal compounds are described in LiquiCryst, LCI Publisher GmbH, Hamburg, Germany, which is a database of liquid crystal compounds. By polymerizing the composition containing a non-polymerizable liquid crystal compound, for example, a composite material of a polymer of the compound (1-2) and the liquid crystal compound can be obtained. In such a composite material, a non-polymerizable liquid crystal compound exists in a polymer network such as a polymer dispersed liquid crystal. Therefore, a liquid crystalline compound having such a property that there is no fluidity in a temperature range to be used is desirable. After curing the inorganic filler, it may be compounded by a method of injecting into the voids in a temperature region showing an isotropic phase, the amount of the liquid crystalline compound calculated to fill the voids in the inorganic filler in advance. After mixing, the inorganic fillers may be polymerized.

[Polymerization initiator]
The composition for a heat dissipation member may include a polymerization initiator as a constituent element. As the polymerization initiator, for example, a photo-radical polymerization initiator, a photo-cationic polymerization initiator, a thermal radical polymerization initiator, or the like may be used depending on the components of the composition and the polymerization method. In particular, a thermal radical polymerization initiator is preferable because the inorganic filler absorbs ultraviolet rays.
Preferred initiators for thermal radical polymerization include, for example, benzoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide Oxide (DTBPO), t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN) and the like. No.

[solvent]
The composition for heat dissipation members may contain a solvent. When the components that need to be polymerized are included in the composition, the polymerization may be performed in a solvent or without a solvent. After the composition containing a solvent is applied onto a substrate by, for example, a spin coating method, the solvent may be removed before photopolymerization. Alternatively, the post-treatment may be performed by heating to an appropriate temperature after photo-curing and thermosetting.
Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone , Cyclohexanone, PGMEA and the like. The above solvents may be used alone or as a mixture of two or more.
It is not meaningful to limit the ratio of the solvent used during the polymerization, and it may be determined for each individual case in consideration of polymerization efficiency, solvent cost, energy cost, and the like.

[Others]
A stabilizer may be added to the composition for a heat radiation member in order to facilitate handling. As such a stabilizer, known stabilizers can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
Further, an additive (such as an oxide) may be added to adjust the viscosity or color of the composition for a heat dissipation member. For example, titanium oxide for whitening, carbon black for blackening, and fine powder of silica for adjusting viscosity can be used. Further, an additive may be added to further increase the mechanical strength. For example, inorganic fibers and cloth such as glass fiber, carbon fiber, and carbon nanotube, or fibers or long molecules such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide can be used as the polymer additive.

[Production method]
Hereinafter, a method for producing a composition for a heat dissipation member and a method for producing a heat dissipation member from the composition will be specifically described.
(1) Coupling Treatment The first inorganic filler is subjected to a coupling treatment to bond one end of the coupling agent to the first inorganic filler. 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. After stirring using a stirrer or the like, the mixture is dried. After the solvent is dried, 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. This solution is separated and purified using a centrifuge. After discarding the supernatant, the same operation is repeated several times by adding a solvent. The inorganic filler subjected to the coupling treatment after the purification is dried using an oven.
(2) Modification with a polymerizable compound A coupling treatment is performed on the second inorganic filler (or the first inorganic filler subjected to the coupling treatment may be used as the second inorganic filler), and a coupling agent is used. Is further bound to a polymerizable compound having two or more functionalities.
As an example, the coupled inorganic filler and the bifunctional or higher functional polymerizable compound are mixed using an agate mortar or the like, and then kneaded using two rolls or the like. Then, it is separated and purified by sonication and centrifugation.
(3) Mixing The first inorganic filler and the second inorganic filler are weighed, for example, so that the weight of the inorganic filler alone becomes 1: 1 and mixed in an agate mortar or the like. Thereafter, mixing is performed using two rolls or the like to obtain a composition for a heat radiation member.
The mixing ratio of the first inorganic filler and the second inorganic filler is such that when the bonding groups forming the bond between the first inorganic filler and the second inorganic filler are each amine: epoxy, the weight of only the inorganic filler is, for example, The weight ratio is preferably from 1: 1 to 1:30, and more preferably from 1: 3 to 1:20. The mixing ratio is determined by the number of terminal bonding groups that form a bond between the first inorganic filler and the second inorganic filler. For example, a secondary amine can react with two oxiranyls. A smaller amount may be used, and the oxiranyl side may be ring-opened, so it is preferable to use a larger amount calculated from the epoxy equivalent.
(4) Manufacturing a heat radiating member As an example, a method of manufacturing a film as a heat radiating member using a composition for a heat radiating member will be described. The composition for a heat radiating member is sandwiched between hot plates using a compression molding machine, and is oriented and cured by compression molding. Further, post-curing is performed using an oven or the like to obtain a heat dissipation member. The pressure at the time of compression molding is preferably 50 to 200 kgf / cm ² , and more preferably 70 to 180 kgf / cm ² . It is preferable that the pressure at the time of curing is basically higher. However, it is preferable to appropriately change the fluidity of the mold and the intended physical properties (such as which direction the thermal conductivity is emphasized) and to apply an appropriate pressure.

Hereinafter, a method for producing a film as a heat radiating member using the composition for a heat radiating member containing a solvent will be specifically described.
First, the composition is applied on a substrate, and the solvent is removed by drying to form a coating layer having a uniform thickness. Examples of the application method include spin coating, roll coating, katen coating, flow coating, printing, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, and meniscus coating.
The solvent can be dried and removed, for example, by air drying at room temperature, drying on a hot plate, drying in a drying furnace, or blowing hot or hot air. The conditions for removing the solvent are not particularly limited, and drying may be performed until the solvent is substantially 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; Inorganic insulating substrate such as aluminum nitride; polyimide, polyamide imide, polyamide, polyether imide, polyether ether ketone, polyether ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate , Polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, Acetyl cellulose or partially saponified product thereof, epoxy resins, phenolic resins, and a 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 a surface treatment such as a saponification treatment, a corona treatment, or a plasma treatment in advance. In addition, you may form a protective layer on these film substrates so that it may not be affected by the solvent contained in the said composition for heat dissipation members. Examples of the material used as the protective layer include polyvinyl alcohol. Further, an anchor coat layer may be formed in order to enhance the adhesion between the protective layer and the substrate. Such an anchor coat layer may be any of inorganic and organic materials as long as it enhances the adhesion between the protective layer and the substrate.

As described above, the case where the bond between the inorganic fillers is constituted by the inorganic filler subjected to the coupling treatment and the inorganic filler which has been subjected to the coupling treatment and modified with the polymerizable compound has been described. Note that it is important in the present invention to realize the bonding between the inorganic fillers as described above, and the coupling agent and the polymerizable compound are bonded in advance using an organic synthesis technique, and then the coupling agent is changed to the second one. You may couple | bond with an inorganic filler. For example, the first inorganic filler is subjected to a coupling treatment with an amino-containing silane coupling agent. Next, the silane coupling agent having vinyl is modified with a polymerizable compound having vinyl and epoxy at the terminals, respectively, and then the second inorganic filler is subjected to coupling treatment with the silane coupling agent. Finally, the amino on the first inorganic filler side is bonded to the epoxy of the polymerizable compound on the second inorganic filler side.
Alternatively, the bond may be formed between the inorganic fillers by using only the inorganic filler further modified with the polymerizable compound after the coupling treatment and bonding the polymerizable compounds together with an appropriate polymerization initiator or the like.

The compound (1-2) is preferable as a heat-radiating material because it has more rings and is less likely to be softened at a higher temperature. As described above, the heat resistance is increased when the polymerizable compound is a polycyclic ring, and the elongation and fluctuation due to heat between the inorganic fillers are small when the linearity is high, and the phonon conduction of heat can be efficiently transmitted, which is preferable. . If the linearity is high in a polycyclic ring, liquid crystallinity is often expressed as a result, so that it can be said that the liquid crystallinity improves heat conduction.
However, it was found that high thermal conductivity and high heat resistance can be obtained also when a bifunctional or higher functional polymerizable compound represented by the above formula (1-1) is used as the bifunctional or higher functional polymerizable compound. Compound (1-1) has a shorter molecular chain, is easier to synthesize, is easier to handle, and is preferable as compared with compound (1-2).

[Heat dissipation member]
The heat radiating member according to the second embodiment of the present invention is obtained by molding a cured product obtained by curing the composition for a heat radiating member according to the first embodiment according to the intended use. This cured product has high thermal conductivity and high heat resistance, a negative or very small positive coefficient of thermal expansion, and is excellent in chemical stability, hardness, mechanical strength, and the like. Here, the mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, flexural modulus, impact strength and the like.
The heat dissipating member of the present invention is useful for a heat dissipating plate, a heat dissipating sheet, a heat dissipating film, a heat dissipating adhesive, a heat dissipating molded product, and the like.

  As the conditions for curing the composition for heat radiation members by thermal polymerization, the heat curing 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 ° C. The range is from seconds to 10 hours, preferably from 1 minute to 5 hours, more preferably from 5 minutes to 1 hour. After the polymerization, it is preferable to gradually cool to suppress stress strain and the like. Further, a reheating treatment may be performed to reduce strain and the like.

  The heat radiating member of the present invention is formed from the composition for a heat radiating member, and is used in the form of a sheet, a film, a thin film, a fiber, a molded article, or the like. Preferred shapes are plates, sheets, films and thin films. In the present specification, the thickness of the sheet is 1 mm or more, the thickness of the film is 5 μm or more, preferably 10 to 500 μm, more preferably 20 to 300 μm, and the thickness of the thin film is less than 5 μm. The film thickness may be appropriately changed depending on the application.

[Electronics]
An electronic device according to the third embodiment of the present invention includes the heat radiating member according to the second embodiment and an electronic device having a heat generating portion. The heat radiating member is disposed on the electronic device so as to contact the heat generating portion. The shape of the heat dissipating member may be any of a heat dissipating electronic substrate, a heat dissipating plate, a heat dissipating sheet, a heat dissipating film, a heat dissipating adhesive, and a heat dissipating molded product.
For example, a semiconductor element can be cited as an electronic device. The heat dissipation member of the present application has high heat resistance and high insulation properties in addition to high heat conductivity. Therefore, it is particularly effective for an insulated gate bipolar transistor (IGBT) that requires a more efficient heat dissipation mechanism due to high power among semiconductor elements. The IGBT is one of the 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 a main conversion element of a high-power inverter, an uninterruptible power supply, a variable voltage variable frequency control device of an AC motor, a control device of a railway vehicle, an electric transport device such as a hybrid car and an electric car, Cookers and the like can be mentioned.

  As described above, the present invention is a composite of an inorganic material and an organic compound, in which an organic compound forms a bond between the inorganic materials, the thermal conductivity and the heat resistance are significantly improved, and the coefficient of thermal expansion can be further controlled. Things. Note that the above functional groups are merely examples, and are not limited to the above functional groups as long as the effects of the present invention can be obtained.

  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.

The component materials constituting the heat radiation member used in the examples of the present invention are as follows.
<Inorganic filler>
-Boron nitride: h-BN particles, manufactured by Momentive Performance Materials Japan (go), (trade name) PolarTherm PTX-25
-Boron nitride: h-BN particles, manufactured by Denka Corporation, (trade name) SGP
-Alumina: manufactured by Denka Corporation, (trade name) DAW-20

・３−アミノプロピルトリエトキシシラン、ＪＮＣ（株）製、（商品名）Ｓ３３０

・３−アミノプロピルトリメトキシシラン、信越化学工業（株）製、（商品名）ＫＢＭ−９０３

・ｐ−アミノフェニルトリメトキシシラン、ＧＥＬＥＳＴ社製、（商品名）ＳＩＡ０５９９．１−ｄ

<Silane coupling agent>
-N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by JNC, (trade name) S320

・ 3-aminopropyltriethoxysilane, manufactured by JNC, (trade name) S330

-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., (trade name) KBM-903

-P-Aminophenyltrimethoxysilane, manufactured by Gelest, (trade name) SIA0599.1-d

・三菱化学（株）製、（商品名）ｊＥＲ ＹＸ４０００Ｈ

・ＪＮＣ（株）製、下記式（１−１３）
下記式（１−１３）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。

<Polymerizable compound>
・ Mitsubishi Chemical Corporation, (trade name) jER YL6121H
The following formulas (1-11) and (1-12) are mixed at a ratio of 1: 1.

・ Mitsubishi Chemical's (product name) jER YX4000H

・ The following formula (1-13) manufactured by JNC Corporation
The following formula (1-13) can be synthesized by the method described in Japanese Patent No. 5084148.

<Definition>
In the following examples, the first inorganic filler combined with the first coupling agent is referred to as filler A (boron nitride + silane coupling agent).
A filler B (boron nitride + silane coupling agent + polymerizable compound), which is a second inorganic filler combined with a second coupling agent and further having a bifunctional or higher functional polymerizable compound bound thereto. And
The combination of the filler A and the filler B is referred to as a heat dissipation member.
FIG. 3 shows a process for producing the filler A, the filler B, and the heat dissipation member.

<Example 1>
-Filler A production step 15 g of boron nitride particles (PolarTherm PTX-25 manufactured by Momentive Performance Materials Japan (go)) and 2.25 g of a silane coupling agent (S320 manufactured by JNC) are added to 100 mL of toluene. The mixture was stirred at 500 rpm for 1 hour using a stirrer, and the obtained mixture was dried at 40 ° C for 4 hours. Further, after the solvent was dried, a heat treatment was performed for 5 hours under a vacuum condition using a vacuum dryer set at 120 ° C. The obtained particles are referred to as filler A.

Filler B preparation step 2 g of Filler A particles and 3.2 g of a polymerizable compound (jER YL6121H manufactured by Mitsubishi Chemical Corporation) were measured and measured using two rolls (IMC-AE00 manufactured by Imoto Seisakusho Co., Ltd.). And mixed at 120 ° C. for 10 minutes. This weight ratio is the number of epoxy rings in which the amino groups of the filler A particles react sufficiently and the amount that both can be sufficiently kneaded on two rolls. The obtained mixture was added to 45 mL of tetrahydrofuran, and after sufficiently stirring, insoluble components were precipitated with a centrifuge (high-speed cooling centrifuge CR22N, manufactured by Hitachi Koki Co., Ltd., 4,000 rpm × 10 min × 25 ° C.). The solution containing the unreacted polymerizable compound dissolved therein was removed by decantation. Subsequently, 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 are referred to as filler B.

Heat dissipating member manufacturing process 0.46 g of filler A and 0.24 g of filler B were measured and mixed, then sandwiched in a stainless steel plate, and used with a compression molding machine (IMC-19EC manufactured by Imoto Machinery Co., Ltd.) set at 150 ° C. Then, the alignment treatment and pre-curing were performed by applying pressure to 30 MPa and continuing the heating state for 15 minutes. That is, when the mixture spreads between the stainless steel plates, the BN particles are plate-like particles, and the particles are oriented so as to be parallel to the stainless steel plates. The amount of the sample was adjusted so that the thickness of the sample was about 300 μm. Further, post-curing was performed at 120 ° C. for 12 hours using an oven. The sample obtained by this operation is used as a heat dissipating member.

<Evaluation>
-Thermogravimetric (TG) measurement The coating amount of the polymerizable compound or the silane coupling agent with respect to the inorganic filler of the filler A, the filler B, and the heat radiation member is a thermogravimetric / differential calorimeter (TG-8121 manufactured by Rigaku Corporation). Was calculated from the loss on heating at 910 ° C.
The 5% weight loss temperature of the heat radiating member was calculated from the temperature at the time of 5% weight reduction when the amount of reduction from 140 ° C. to 900 ° C. was taken as 100% by weight using the above-described measuring device.
-Evaluation of coefficient of thermal expansion A test piece of 3 x 15 mm was cut out from the obtained sample, and the coefficient of thermal expansion was determined in the range of 50 to 200 ° C. The coefficient of thermal expansion was measured with a TMA-SS6100 thermomechanical analyzer manufactured by SII Corporation.
-Evaluation of color From the obtained sample, a 15 x 15 mm test piece was cut out and the color was measured. The color was measured with a spectrophotometer SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.

<Example 2>
In Example 2, the heating temperature of the two rolls in the filler B step was 150 ° C.

<Examples 3 and 4>
In Examples 3 and 4, a polymerizable compound jER YX4000H manufactured by Mitsubishi Chemical Corporation was used.
In Example 4, the two-roll heating temperature in the filler B step was set to 150 ° C.

<Examples 5 to 12>
In Examples 5 to 12, SGP manufactured by Denka Corporation was used for BN particles.
As the silane coupling agent in Examples 5 and 6, KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd. was used.
As the silane coupling agent in Examples 7 to 12, S330 manufactured by JNC Co., Ltd. was used.

<Example 13>
As the silane coupling agent of Example 13, SIA0599.1-d (p-aminophenyltrimethoxysilane) manufactured by Gelest was used.
-Filler A preparation step 7 g of boron nitride particles (SGP manufactured by Denka Co., Ltd.) and 0.36 g of a silane coupling agent (SIA0599.1-d) were added to 20 mL of methanol and 50 mL of water, and the mixture was stirred at 920 rpm using a stirrer at 60 ° C. For 1 hour, and the resulting mixture was left overnight. Further, after the solvent was dried, a heat treatment was performed for 5 hours under a vacuum condition using a vacuum dryer set at 120 ° C. The obtained particles are referred to as filler A.
-Filler B preparation step 2.56 g of filler A particles and 4.8 g of a polymerizable compound (jER YX4000H manufactured by Mitsubishi Chemical Corporation) are measured and rolled into two rolls (IMC-AE00 manufactured by Imoto Seisakusho). And mixed at 180 ° C. for 10 minutes. This weight ratio is the number of epoxy rings in which the amino groups of the filler A particles react sufficiently and the amount that both can be sufficiently kneaded on two rolls. The obtained mixture was added to 45 mL of tetrahydrofuran, and after sufficiently stirring, insoluble components were precipitated with a centrifuge (high-speed cooling centrifuge CR22N, manufactured by Hitachi Koki Co., Ltd., 4,000 rpm × 10 min × 25 ° C.). The solution containing the unreacted polymerizable compound dissolved therein was removed by decantation. Subsequently, 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 are referred to as filler B.

<Example 14>
In Example 14, alumina (DAW-20 manufactured by Denka Corporation) was used as the inorganic filler particles.

<Comparative Examples 1 and 2>
In Comparative Examples 1 and 2, SGP manufactured by Denka Corporation was used as BN particles.
As the silane coupling agent of Comparative Example 1, KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd. was used.
As the silane coupling agent of Comparative Example 2, SNC manufactured by JNC Co., Ltd. was used.
Formula (1-13) manufactured by JNC Co., Ltd. was used as a polymerizable compound to be crosslinked.

<Comparative Example 3>
Comparative Example 3 was the same as Comparative Example 2, except that alumina (DAW20 manufactured by Denka Corporation) was used as the inorganic filler particles.

  The 5% weight loss temperatures of Examples 1 to 14 all were higher than those of Comparative Examples 1 to 3. It is considered that the structure of the organic components (polymerizable compound and silane coupling agent) in the examples has a small number of substituents and is hardly affected by heat, so that the heat radiation member has improved heat resistance. Further, positive and negative coefficients of thermal expansion of Examples 1 to 14 are mixed, and the thermal expansion of the heat radiation member can be controlled by the combination. Further, the lightness of L * of Examples 1 to 14 is increased as compared with Comparative Examples 1 to 3. It is considered that the organic components of the examples had less substituents than the comparative examples, and the organic components were prevented from being colored due to oxidation and the whiteness was increased. Although the polymerizable compound used in Examples 1 to 14 has a shorter molecular chain than the polymerizable compound expressing liquid crystallinity, the heat dissipating members of Examples 1 to 14 may have high thermal conductivity and high heat resistance. it can.

  All publications, including publications, patent applications, and patents, cited herein are specifically incorporated by reference, and each publication is individually incorporated by reference, and all of its contents are to the same extent as described herein. And incorporated here by reference.

  The use of nouns and similar descriptive terms used in connection with the description of the present invention, particularly with reference to the following claims, unless otherwise indicated herein or otherwise clearly contradicted by context. , Singular and plural. The terms "comprising," "having," "including," and "including" are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. The recitation of numerical ranges herein is merely intended to serve as an abbreviation for individually referring to each value falling within the range, unless otherwise indicated herein. And each value is incorporated into the specification as if individually listed herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by context. Any use of the example or illustrative language herein (eg, "such as") is intended solely to better describe the invention and, unless otherwise stated, places limitations on the scope of the invention. is not. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

  This specification describes preferred embodiments of the present invention, including the best mode known to the inventors for carrying out the invention. Modifications of these preferred embodiments will become apparent to those skilled in the art upon reading the above description. The present inventor anticipates that the skilled artisan will apply such modifications as appropriate, and envisions that the present invention may be practiced otherwise than as specifically described herein. . Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all variations is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

DESCRIPTION OF SYMBOLS 1 1st inorganic filler, boron nitride 2 2nd inorganic filler, boron nitride 11 1st coupling agent 12 2nd coupling agent 22 Polymerizable compound

Claims (8)

A thermally conductive first inorganic filler coupled to one end of the first coupling agent;
A second inorganic filler having thermal conductivity bonded to one end of a second coupling agent, wherein a bifunctional or higher functional polymerizable compound is further bonded to the other end of the second coupling agent. And a filler;
The second coupling agent has a polymerizable compound represented by the following formula (1-1) bonded as the polymerizable compound having two or more functional groups,
The polymerizable compound is a non-liquid crystalline compound,
At least one of the functional groups of the polymerizable compound is capable of bonding to the other end of the first coupling agent.
A composition for a heat dissipation member.

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

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

[In the formulas (2-4) to (2-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms. ] The first inorganic filler and the second inorganic filler are bonded with a silane coupling agent represented by the following formula (3-1) as the first coupling agent and the second coupling agent. ,
The composition for a heat dissipation member according to claim 1.

_{^{(R 1 -O) j -Si (}} R 5) 3-j - (R 2) k - (R 3) k - (R 4) k -Ry
(3-1)
[In the above formula (3-1),
R ¹ is H—, or CH ₃ — (CH ₂ ) ₀ — ₄ —;
R ² _is, - _{(CH 2) 0~3} -O- and is;
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} - a and;
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;
Formula (3-1) includes at least one of R ³ and R ⁴ . ] The first inorganic filler and the second inorganic filler are respectively boron nitride, boron carbide, carbon nitride boron, graphite, carbon fiber, carbon nanotube, graphene, alumina, aluminum nitride, silica, silicon nitride, silicon carbide, Zinc oxide, magnesium oxide, magnesium hydroxide, cordierite, or at least one selected from iron oxide-based materials,
The composition for a heat dissipation member according to claim 1. A third inorganic filler having a different coefficient of thermal expansion from the first inorganic filler and the second inorganic filler;
The composition for a heat dissipation member according to any one of claims 1 to 3. An organic compound or a polymer compound that is not bonded to the first inorganic filler and the second inorganic filler;
The composition for a heat dissipation member according to any one of claims 1 to 4. The composition for a heat radiating member according to any one of claims 1 to 5 is cured,
Heat dissipation member. A heat dissipation member according to claim 6;
An electronic device having a heating unit;
The heat dissipating member is disposed on the electronic device so as to contact the heat generating portion,
Electronics. Bonding a thermally conductive first inorganic filler to one end of the first coupling agent;
Bonding a thermally conductive second inorganic filler to one end of the second coupling agent;
Bonding the other end of the second coupling agent to a bifunctional or higher functional polymerizable compound;
Bonding the other end of the first coupling agent to the bifunctional or higher functional polymerizable compound;
The bifunctional or higher functional polymerizable compound is a polymerizable compound represented by the following formula (1-1),
The polymerizable compound is a non-liquid crystalline compound,
Manufacturing method of heat dissipation member.

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

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

[In the formulas (2-4) to (2-6), R ^{7 to} R ¹⁰ are each independently hydrogen or alkylene having 1 to 20 carbon atoms. ]

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