JPWO2019188973A1 - Compositions, heat dissipation members, electronic devices, and methods for manufacturing compositions - Google Patents

Abstract

One embodiment of the present invention relates to a composition, a heat radiating member, an electronic device, and a method for producing the composition, wherein the composition comprises a composite material A1 in which a coupling agent A is bonded to a first filler and hydroxy. Includes a polymer containing a ring having.

Description

One embodiment of the present invention relates to a composition, a heat radiating member, an electronic device, and a method for producing the composition.

In recent years, in semiconductor elements for power control of hybrid vehicles and electric vehicles, CPUs for high-speed computers, etc., the materials constituting them have been made highly thermally conductive so that the temperature of the internal semiconductors does not become too high. The ability to effectively release (dissipate) heat to the outside is important.

As an example of the heat dissipation method, there is a method in which a high thermal conductive material (heat dissipation member) is brought into contact with a heat generating portion to guide heat to the outside and dissipate heat. Examples of such highly thermally conductive materials include metal materials such as metals and inorganic materials such as metal oxides, but these inorganic materials have problems in processability and fragility, and are useful as heat radiating materials. It cannot be said that there is.

In order to solve these problems, a heat radiating member which is made by mixing a resin and an inorganic material and having high thermal conductivity is being developed. For example, Patent Document 1 discloses a phenol resin molding material containing a phenol resin and boron nitride in a predetermined ratio.

Japanese Unexamined Patent Publication No. 2006-096858

However, a molded product (heat dissipation member) obtained by mixing a conventional resin and an inorganic material as described in Patent Document 1 tends to have insufficient thermal conductivity, and has further high thermal conductivity. Is required.

Further, in recent years, due to miniaturization, high integration, high power, etc., the heat radiating member is required to have high heat radiating property and high reliability, and specifically, a predetermined effect even at a high temperature. Heat resistance is required for high reliability.

One embodiment of the present invention provides a heat radiating member excellent in high thermal conductivity and high heat resistance in a well-balanced manner, and a composition capable of forming the heat radiating member.

The present inventors have diligently studied to solve the above-mentioned problems. As a result, they have found that the above problems can be solved according to the following configuration example, and have completed the present invention.
The configuration example of the present invention is as follows.

[1] Composite material A1 in which the coupling agent A is bonded to the first filler, and
A composition comprising a polymer containing a ring having a hydroxy.

[2] Composite material B1 in which the coupling agent B is bonded to the second filler, and
Composite material B2 in which a second filler is bonded to one end of the coupling agent B and a reactive compound is bonded to the other end.
The composition according to [1], further comprising at least one selected from.

[3] The composition according to [1] or [2], wherein the polymer is a polymer having at least one of the structures represented by the formulas (1) and (2).

［式（１）中、ｍは、平均値で２〜１００であり；
ｎは独立に、平均値で１以上であり；
Ｒ¹は独立に、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、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、または４，４’−（９−フルオレニリデン）ジフェニレンであり、
炭素数１〜１０のアルキレンにおいて、少なくとも１つの水素は−ＣＨ₃またはヒドロキシ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、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、および４，４’−（９−フルオレニリデン）ジフェニレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ＝は、−Ｎ＝で置き換えられてもよく、少なくとも１つの水素は、ヒドロキシ、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、該炭素数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における少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく；
環Ａ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、および９，９−ジフェニルフルオレンから選ばれる環から、少なくとも２つの水素を除いた基であり、
これらの基において、少なくとも１つの−ＣＨ＝は、−Ｎ＝で置き換えられてもよく、少なくとも１つの水素は、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、該炭素数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ける少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよい。］

[In equation (1), m has an average value of 2 to 100;
n is independently greater than or equal to 1 on average;
R ¹ is independently alkylene, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octo-1 having 1 to 10 carbon atoms. , 4-diyl, bicyclo [3.1.0] hex-3,6-diyl, or 4,4'-(9-fluorenelilidene) diphenylene.
In the alkylene with 1 to 10 carbon atoms, at least one hydrogen may be replaced with _{-CH 3 or hydroxy.}
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octo-1,4-diyl, bicyclo [3.1.0] hex In −3,6-diyl, and 4,4'-(9-fluorenelilidene) diphenylene, at least one −CH ₂ − may be replaced by −O−, and at least one −CH = is −N. It may be replaced with =, and at least one hydrogen may be replaced with hydroxy, halogen, an alkyl having 1 to 10 carbon atoms, or an alkyl halide having 1 to 10 carbon atoms, and the hydrogen having 1 to 10 carbon atoms. _{At least one −CH 2} − in an alkyl or an alkyl halide having 1 to 10 carbon atoms may be replaced with −O−, −CO−, −COO−, or −OCO−;
Ring A is a group from which at least two hydrogens have been removed from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, and 9,9-diphenylfluorene.
In these groups, at least one -CH = may be replaced with -N = and at least one hydrogen is a halogen, an alkyl having 1-3 carbon atoms, or an alkyl halide having 1-3 carbon atoms. _{May be replaced, at least one −CH 2} − in the alkyl having 1-3 carbon atoms or the alkyl halide having 1-3 carbon atoms is −O−, −CO−, −COO−, or −OCO−. May be replaced with. ]

［式（２）中、ｍは、平均値で２〜１００であり；
ｎは独立に、平均値で１以上であり、；
環Ｂは独立に、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、および９，９−ジフェニルフルオレンから選ばれる環から、少なくとも３つの水素を除いた基であり、
これらの基において、少なくとも１つの−ＣＨ＝は、−Ｎ＝で置き換えられてもよく、少なくとも１つの水素は、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、該炭素数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ける少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく；
Ｒ²およびＲ⁴はそれぞれ独立に、単結合または炭素数１〜５のアルキレンであり、
該アルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの水素は−ＣＨ₃または−ＯＨで置き換えられてもよく；
Ｒ³は独立に、単結合、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、１，１’−ビフェニル−４，４’−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、または４，４’−（９−フルオレニリデン）ジフェニレンであり、
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、１，１’−ビフェニル−４，４’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、および４，４’−（９−フルオレニリデン）ジフェニレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ＝は、−Ｎ＝で置き換えられてもよく、少なくとも１つの水素は、ヒドロキシ、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、該炭素数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における少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよい。］

[In equation (2), m has an average value of 2 to 100;
n is independently greater than or equal to 1 on average;
Ring B is an independent group from which at least three hydrogens have been removed from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, and 9,9-diphenylfluorene.
In these groups, at least one -CH = may be replaced with -N = and at least one hydrogen is a halogen, an alkyl having 1-3 carbon atoms, or an alkyl halide having 1-3 carbon atoms. _{May be replaced, at least one −CH 2} − in the alkyl having 1-3 carbon atoms or the alkyl halide having 1-3 carbon atoms is −O−, −CO−, −COO−, or −OCO−. May be replaced by;
R ² and R ⁴ are independently single bonds or alkylenes having 1 to 5 carbon atoms.
In the alkylene, at least one −CH ₂ − may be replaced by −O−, −S−, −CO−, −COO−, or −OCO−, and at least one hydrogen is −CH ₃ or −. May be replaced by OH;
R ³ is independently single-bonded, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, 1,1'-biphenyl-4,4'-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, or 4,4'-(9-fluorenelilidene) diphenylene.
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, 1,1'-biphenyl-4,4'diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Oct-1, In 4-diyl, bicyclo [3.1.0] hex-3,6-diyl, and 4,4'-(9-fluorenelilidene) diphenylene, at least one -CH ₂ -is replaced by -O-. Also, at least one -CH = may be replaced with -N =, and at least one hydrogen is hydroxy, halogen, alkyl having 1 to 10 carbon atoms, or alkyl halide having 1 to 10 carbon atoms. _{It may be replaced by at least one −CH 2} − in the alkyl having 1 to 10 carbon atoms or the alkyl halide having 1 to 10 carbon atoms being −O−, −CO−, −COO−, or −OCO−. May be replaced with. ]

[4] The composition according to any one of [1] to [3], wherein the polymer is a polymer having a hydroxy bonded to an aromatic ring in the side chain.

[5] In the above formula (1),
R ¹ is independently an alkylene, cyclohexylene, cyclohexenylene, phenylene, or naphthalene-2,6-diyl having 1 to 10 carbon atoms.
Ring A is a group that independently removes at least two hydrogens from benzene or naphthalene.
The composition according to [3].

[6] In the formula (2),
Ring B is independently a group of benzene or naphthalene from which at least three hydrogens have been removed.
R ³ is independently a single bond, cyclohexylene, phenylene, naphthalene-2,6-diyl, or 1,1'-biphenyl-4,4'diyl,
The composition according to [3].

[7] The polymer according to any one of [1] to [6], wherein the polymer contains a structure derived from a ring-free monomer having at least one hydroxy selected from a (meth) acrylic compound and a vinyl compound. Composition.

[8] The composition according to any one of [1] to [7], wherein the filler is an inorganic filler selected from oxides, nitrides, carbides, and carbon materials.
[9] The filler is at least one selected from alumina, silica, titania, zirconia, cordierite, boron nitride, boron carbide, carbon nitride carbon, graphite, carbon fibers, carbon nanotubes, and graphene, [1]. ] To [8].

[10] The composition according to any one of [1] to [9], wherein the coupling agent contains oxylanyl or oxetanyl.

[11] The composition according to any one of [1] to [10], which comprises an organic compound which is not bonded to the filler (however, it is a compound other than a polymer containing a ring having a hydroxy).

[12] The composition according to any one of [1] to [11], which is used for a heat radiating member.
[13] A heat radiating member obtained by curing the composition according to any one of [1] to [12].

[14] The heat radiating member according to [13] and an electronic device having a heat generating portion are provided.
An electronic device arranged in the electronic device so that the heat radiating member comes into contact with the heat generating portion.

[15] A step a of combining the first filler and the coupling agent A to obtain the composite material A1 and
A method for producing a composition, which comprises the composite material A1 obtained in the step a and the step c1 in which a polymer containing a ring having a hydroxy is mixed.

[16] A step a of combining the first filler and the coupling agent A to obtain the composite material A1 and
Step b1 of combining the second filler and the coupling agent B to obtain the composite material B1, or
The second filler and one end of the coupling agent B are bonded, and then the other end of the coupling agent B is bonded to the reactive compound, or one end of the coupling agent B and the reactive compound are bonded. Then, the other end of the coupling agent B is bonded to the second filler to obtain the composite material B2, and the step b2.
A step c2 of mixing the composite material A1 obtained in step a, the composite material B1 obtained in step b1 or the composite material B2 obtained in step b2, and a polymer containing a ring having a hydroxy is included. Method for producing composition.

According to one embodiment of the present invention, it is possible to provide a heat radiating member having excellent heat conductivity and high heat resistance in a well-balanced manner. Further, it is also possible to provide a heat radiating member having excellent chemical stability, hardness, mechanical strength and the like.

FIG. 1 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 1. FIG. 2 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 2. FIG. 3 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 3. FIG. 4 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 4. FIG. 5 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 5. FIG. 6 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 6. FIG. 7 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Example 7. FIG. 8 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Comparative Example 1. FIG. 9 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Comparative Example 2. FIG. 10 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Comparative Example 3. FIG. 11 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Comparative Example 4. FIG. 12 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Comparative Example 5. FIG. 13 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Comparative Example 6. FIG. 14 is a graph showing the thermal expansion behavior of the heat radiating member manufactured in Reference Example 1.

The present invention will be specifically described with reference to the following detailed description, but the present invention is not limited to the following description.

≪Composition≫
The composition according to one embodiment of the present invention (hereinafter, also referred to as “the present composition”) comprises a composite material A1 in which a coupling agent A is bonded to a first filler, and a polymer containing a ring having hydroxy. including.
Since the present composition contains a composite material in which a filler and a coupling agent or the like are bonded in advance, the filler and the coupling agent or the like are simply mixed without containing such a composite material. It has the above-mentioned effect, which is different from the composition prepared in 1.

In one embodiment in which the present composition is cured, the fillers react with each other with a coupling agent and a polymer (the coupling agent and the polymer referred to herein have a reactive group (eg, oxylanyl or hydroxy) reacted with each other. It is possible to obtain a heat radiating member containing a composite that is three-dimensionally bonded via (the same applies hereinafter) or through a coupling agent and a polymer and / or a reactive compound. It is considered that the heat radiating member including such a composite exhibits high thermal conductivity not only in the horizontal direction but also in the thickness direction.

The present composition preferably does not have highly polar aminos, amides, etc. from the viewpoint that a heat radiating member having low hygroscopicity can be easily obtained. In such a composition, as a raw material to be used, a raw material having no amino or amide may be used, or the amino or amide may be eliminated by curing or the like when forming a heat radiating member.

As one aspect of the present composition, the composite material B1 in which the coupling agent B is bonded to the second filler, and the second filler is bonded to one end of the coupling agent B and the reactive compound is bonded to the other end. It is also preferable to further contain at least one selected from the composite material B2.
In one embodiment using the composite material A1 and the composite materials B1 and B2, the first filler and the second filler dissipate heat including a composite bonded via a coupling agent, a reactive compound and / or a polymer. Members can be obtained. In such a composite, since the fillers are directly bonded to each other, it is considered that the heat radiating member containing the composite exhibits high thermal conductivity.

<Filler>
The first and second fillers are not particularly limited, and may be an inorganic filler or an organic filler, and conventionally known fillers can be used.
The first and second fillers may be different fillers, but may be the same filler because only "first" and "second" are added for the purpose of clarifying the wording.

Examples of the filler include oxidation of alumina, magnesia, beryllia, silica, titania, zirconia, zinc oxide, cordierite, copper oxide, cerium oxide, yttrium oxide, tin oxide, forminium oxide, bismuth oxide, cobalt oxide, calcium oxide and the like. Materials; Nitridees such as boron nitride, aluminum nitride, silicon nitride, and carbon nitride; Carbides such as boron carbide and silicon carbide; Carbon materials such as diamond, graphite, carbon fiber, carbon nanotubes, and graphene; Magnesium hydroxide, hydroxide Hydroxides such as aluminum; metals such as silicon, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, and stainless steel; inorganic fibers such as glass fiber and carbon fiber and their cloths. Examples include organic fillers such as fibers or particles made of polyvinyl formal, polyvinyl butyral, polyester, polyamide, polyimide and the like.
Among these, an inorganic filler selected from oxides, nitrides, carbides, and carbon materials is preferable from the viewpoint that a heat radiating member having more excellent thermal conductivity can be easily obtained.

The filler includes alumina, silica, titania, zirconia, cordierite, boron nitride, boron carbide, carbon nitride carbon, graphite, and carbon from the viewpoints of thermal conductivity, availability, and bondability with a coupling agent. Fibers, carbon nanotubes, and graphene are preferred.
Further, when these fillers are used, it is possible to easily obtain a heat radiating member having a high thermal conductivity and a very small or negative thermal expansion coefficient.

The composition preferably contains an inorganic filler having high thermal conductivity. Examples of the highly thermally conductive inorganic filler include boron nitride, aluminum nitride, silicon nitride, carbon nitride carbon, boron carbide, silicon carbide, diamond, graphite, carbon fibers, carbon nanotubes, beryllia, magnesia, and alumina.

The first and second fillers are preferably boron nitride, boron carbide, carbon nitride carbon, graphite, carbon fibers, carbon nanotubes, and graphene. As the first and second fillers, hexagonal boron nitride (h-BN) and graphite are preferable because the thermal conductivity in the plane direction is very high, and h-BN in particular has a low dielectric constant. It is preferable because it has high insulation properties. Further, for example, it is preferable to use a plate-shaped filler such as h-BN or graphite because the plate-shaped structure can be oriented along a mold or the like at the time of molding or curing.

The type, shape, size, etc. of the filler can be appropriately selected according to the purpose, and examples of the shape of the filler include a plate (flat) shape, a spherical shape, an amorphous shape, a fibrous shape, a rod shape, and a tubular shape. ..

The average particle size of the filler is preferably 0.1 to 500 μm, more preferably 1 to 200 μm, from the viewpoint that a heat radiating member having better thermal conductivity can be easily obtained.
The average particle size in the present specification is a median diameter based on the particle size distribution measurement by the laser diffraction / scattering method. Further, the average particle size means the average value of the lengths of the long sides when the shape of the filler is plate-shaped, and the average value of the fiber lengths and rod lengths when the filler is fibrous or rod-shaped. Say that.

The content of the filler in the present composition is preferably 50 to 98% by weight, more preferably 60 to 97, from the viewpoint that a heat radiating member having excellent balance of high thermal conductivity and high heat resistance can be easily obtained. It is% by weight, particularly preferably 70 to 95% by weight.
This composition having a filler content in the above range is different from the conventional composition in which a filler is added to an organic component such as a resin, and an organic such as a coupling agent, a polymer, and a reactive compound is provided between the fillers. It can be said that the composition is such that the component is present, more specifically, the organic component connects the fillers.
The amount of the composite material A1, the composite material B1, and the composite material B2 used is preferably such that the content of the filler is within the above range.

<Coupling agent>
The coupling agents (coupling agents A and B) used in this composition are compounds having at least two reactive groups and capable of binding to a filler. Further, the coupling agent is preferably a compound capable of reacting with hydroxy.
Coupling agents A and B may be different coupling agents, but the same coupling agent may be used because "A", "B", etc. are only added for the purpose of clarifying the wording. Good.

The coupling agent is not particularly limited, and known coupling agents such as a silane-based coupling agent, a titanate-based coupling agent, and an aluminate-based coupling agent can be used. Among these, the silane-based coupling agent is used. preferable.

Since the coupling agent used in this composition binds to the filler, it preferably contains a hydrolyzable group such as alkoxy capable of binding.
Further, the coupling agent used in this composition preferably reacts with hydroxy, and more preferably does not react with hydroxy to form a highly polar amide bond or urethane bond. Therefore, oxylanyl or oxetanyl, particularly, It is preferable to have oxylanyl.
The coupling agent used in this composition preferably does not have amino and amide from the viewpoint that a heat radiating member having lower hygroscopicity can be easily obtained.

Examples of the coupling agent having oxylanyl or oxetanyl include Sila Ace (trade name) S510 and S530 manufactured by JNC Co., Ltd.

The amount of reaction of the coupling agent to the filler varies mainly depending on the size of the filler and the reactivity of the coupling agent used, so it is difficult to specify.
It is preferable to bind as many coupling agents as possible to the filler so that the number of reactive groups of the coupling agent that reacts with the reactive groups is the same as or slightly larger than the number of reactive groups of the filler. It is preferable to use a coupling agent.
The amount of the coupling agent bonded to 100 parts by weight of the filler is preferably 1 to 30 parts by weight, more preferably 2 from the viewpoint of easily obtaining a heat radiating member having a good balance of high thermal conductivity and high heat resistance. It is ~ 25 parts by weight, more preferably 3 to 20 parts by weight.

<Polymer>
The composition comprises a polymer containing a ring having a hydroxy. By using such a polymer, it is possible to easily obtain a heat radiating member having a good balance of high thermal conductivity and high heat resistance.
The hydroxy may be directly bonded to the ring or may be bonded via a predetermined bonding group, but the above effect can be more exerted, and a heat radiating member particularly excellent in thermal conductivity can be easily obtained. It is preferable that it is directly bonded to the ring from the viewpoint of being able to be formed.
Further, the ring is preferably an aromatic ring (including a complex aromatic ring) from the viewpoint that the above-mentioned effect is more exhibited and a heat-dissipating member having particularly excellent heat resistance and the like can be easily obtained. The polymer is particularly preferably a polymer having a hydroxy (phenolic hydroxy) bonded to an aromatic ring in the side chain.
The polymer in the present specification refers to a compound having two or more repeating units (for example, a structure in which m is repeated in the formula (1)).
One kind of polymer may be used for this composition, and two or more kinds of polymers may be used.

The polymer is not particularly limited as long as it contains a ring having hydroxy, but the formula (1) or (2) or (2) can be easily obtained in a well-balanced manner due to high thermal conductivity and high heat resistance. ) Is preferably a polymer containing the structure represented by).
The polymer may be a polymer containing both a structure represented by the formula (1) and a structure represented by the formula (2), or may be a polymer containing either one.

The content of the structures represented by the formulas (1) and (2) in the polymer is 100% by weight of the polymer from the viewpoint that a heat radiating member having better thermal conductivity and heat resistance can be easily obtained. On the other hand, it is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.

In the formula (1), m has an average value of 2 to 100, preferably an average value of 4 to 80.
In the formula (1), n independently has an average value of 1 or more, preferably 1.
The substitution position of the hydroxy bonded to the ring A is not particularly limited, but for example, when n is 1, the substitution position of the hydroxy with respect to the CH to which the ring A is bonded is preferably the ortho position or the para position, and more preferably the para position.

The "mean value of m" means the average value of the portion corresponding to m in the case where the polymer may exist with a certain distribution. Similar statements herein have similar meanings.
“N is independent” means that when m is 2 or more, there are two or more n in the equation (1), but in this case, the two or more n may be the same or different. It means good. Similar statements herein have similar meanings.
Further, in a certain expression in the present specification, when two or more identical codes are present, or when two or more identical codes are present in different expressions, the groups represented by these codes may be the same or different. Good.

In formula (1), R ¹ is independently alkylene, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2] having 1 to 10 carbon atoms. .2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, or 4,4'-(9-fluorenelilidene) diphenylene.
In the alkylene with 1 to 10 carbon atoms, at least one hydrogen may be replaced with _{-CH 3 or hydroxy.}
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octo-1,4-diyl, bicyclo [3.1.0] hex In −3,6-diyl, and 4,4'-(9-fluorenelilidene) diphenylene, at least one −CH ₂ − may be replaced by −O−, and at least one −CH = is −N. It may be replaced with =, and at least one hydrogen may be replaced with hydroxy, halogen, an alkyl having 1 to 10 carbon atoms, or an alkyl halide having 1 to 10 carbon atoms, and the hydrogen having 1 to 10 carbon atoms. _{At least one −CH 2} − in an alkyl or an alkyl halide having 1 to 10 carbon atoms may be replaced with −O−, −CO−, −COO−, or −OCO−.

The word "at least one" means "at least one selected indiscriminately", but usually a structure that is difficult to adopt based on common sense in the field, for example, oxygen and oxygen adjacent to each other-O- It is preferable not to include O-.

From the viewpoint that a heat radiating member having excellent flexibility can be easily obtained, R ¹ is preferably alkylene, cyclohexylene, or cyclohexenylene having 1 to 10 carbon atoms independently, and has heat resistance and thermal conductivity. Phenylene or naphthalene-2,6-diyl is preferable for ^{R 1} independently from the viewpoint that an excellent heat radiating member can be easily obtained.

In formula (1), ring A is a group obtained by removing at least two hydrogens from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, and 9,9-diphenylfluorene.
In these groups, at least one -CH = may be replaced with -N = and at least one hydrogen is a halogen, an alkyl having 1-3 carbon atoms, or an alkyl halide having 1-3 carbon atoms. _{May be replaced, at least one −CH 2} − in the alkyl having 1-3 carbon atoms or the alkyl halide having 1-3 carbon atoms is −O−, −CO−, −COO−, or −OCO−. May be replaced with.
Among these, the ring A is preferably a group obtained by removing at least two hydrogens from benzene or naphthalene independently from the viewpoint that a heat radiating member having more excellent heat resistance can be easily obtained, and from benzene. More preferably, it is a group from which at least two, preferably two hydrogens have been removed.

The polymer containing the structure represented by the formula (1) can be synthesized by a conventionally known method, and for example, a compound having a polymerizable group such as vinyl and a ring having a hydroxy such as hydroxyphenyl, specifically. Specifically, it can be synthesized using vinylphenol or the like.

In the formula (2), m has an average value of 2 to 100, preferably an average value of 4 to 80.
In the formula (2), n independently has an average value of 1 or more, preferably 1.

Ring B is an independent group from which at least three hydrogens have been removed from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, and 9,9-diphenylfluorene.
In these groups, at least one -CH = may be replaced with -N = and at least one hydrogen is a halogen, an alkyl having 1-3 carbon atoms, or an alkyl halide having 1-3 carbon atoms. _{May be replaced, at least one −CH 2} − in the alkyl having 1-3 carbon atoms or the alkyl halide having 1-3 carbon atoms is −O−, −CO−, −COO−, or −OCO−. May be replaced with.
Among these, the ring B is preferably a group obtained by removing at least three hydrogens from benzene or naphthalene independently from the viewpoint that a heat radiating member having more excellent heat resistance can be easily obtained, and from benzene. More preferably, it is a group excluding at least three, preferably three hydrogens.

R ² and R ⁴ are independently single bonds or alkylenes having 1 to 5 carbon atoms.
In the alkylene, at least one −CH ₂ − may be replaced by −O−, −S−, −CO−, −COO−, or −OCO−, and at least one hydrogen is −CH ₃ or −. It may be replaced by OH.
Increasing the number of carbon atoms in the alkylene makes it easier to obtain a heat-dissipating member with excellent flexibility, but the thermal conductivity tends to decrease. Therefore, R ² and R ⁴ are independently single-bonded and have 1 to 5 carbon atoms. It is preferable to combine them appropriately.

R ³ is independently single-bonded, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, 1,1'-biphenyl-4,4'-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, or 4,4'-(9-fluorenelilidene) diphenylene.
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, 1,1'-biphenyl-4,4'diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Oct-1, In 4-diyl, bicyclo [3.1.0] hex-3,6-diyl, and 4,4'-(9-fluorenelilidene) diphenylene, at least one -CH ₂ -is replaced by -O-. Also, at least one -CH = may be replaced with -N =, and at least one hydrogen is hydroxy, halogen, alkyl having 1 to 10 carbon atoms, or alkyl halide having 1 to 10 carbon atoms. _{It may be replaced by at least one −CH 2} − in the alkyl having 1 to 10 carbon atoms or the alkyl halide having 1 to 10 carbon atoms being −O−, −CO−, −COO−, or −OCO−. May be replaced with.

From the viewpoint of improving the heat resistance and thermal conductivity of the obtained heat-dissipating member, R ³ is independently single-bonded, cyclohexylene, phenylene, naphthalene-2,6-diyl, or 1,1'-biphenyl-4,4. 'Diyl is preferred, with single bonds, phenylene, or naphthalene-2,6-diyl being more preferred.

The polymer containing the structure represented by the formula (2) can be synthesized by a conventionally known method. For example, it is synthesized by reacting a cyclic compound having a hydroxy such as phenol or cresol with formaldehyde or the like. can do.

In addition to the structures represented by the formulas (1) and (2), the polymer may have a structure derived from a monomer (polymerizable compound) that does not contain a ring having hydroxy.
The ring-free monomer having hydroxy may be a monofunctional compound or a bifunctional or higher functional compound, for example, a (meth) acrylic compound such as a (meth) acrylic acid alkyl ester, ethylene, propylene, styrene, or acetic acid. Examples include vinyl compounds such as vinyl.
It should be noted that the monomer that does not contain the hydroxy ring does not contain the hydroxy ring, and the monomer may contain a hydroxy that is not bonded to the ring or a ring that does not have hydroxy.

When the polymer contains a structure derived from a monomer that does not contain a ring having a hydroxy, the polymer does not contain a ring having a hydroxy from the viewpoint that a heat-dissipating member having better heat resistance can be easily obtained. The content of the structure derived from the monomer is preferably 1 to 95% by weight, more preferably 5 to 80% by weight, based on 100% by weight of the polymer.

A polymer having a structure derived from a monomer having a hydroxy and not containing a ring can be synthesized by a conventionally known method. For example, a compound such as vinylphenol that induces a structure represented by the formulas (1) and (2) is polymerized. At that time, polymerization may be carried out using a monomer that does not contain a ring having hydroxy, and after synthesizing a compound having a structure represented by the formulas (1) and (2), the compound and a ring having hydroxy are combined. It may be polymerized with a monomer not contained.

A commercially available product may be used as the polymer, and examples of the polymer having the structure represented by the formula (1) include polyvinylphenol resin (Marcalinker series manufactured by Maruzen Petrochemical Co., Ltd.). Examples of the polymer having the structure represented by the formula (2) include conventionally known phenolic resins such as phenol novolac resin, alkylphenol novolac resin, resol resin, and cresol novolac resin.

The content of the polymer in the present composition is preferably 0.1 to 49% by weight, more preferably, from the viewpoint that a heat radiating member having excellent balance of high thermal conductivity and high heat resistance can be easily obtained. Is 0.5 to 30% by weight.

<Reactive compound>
The reactive compound is not particularly limited as long as it is a polymerizable compound capable of binding to the coupling agent and forming the composite material B2.
The reactive compound used in this composition may be one kind or two or more kinds.

The reactive compound used as the raw material of the composite material B2 is preferably a bifunctional or higher functional compound, and is preferably trifunctional or higher or tetrafunctional, from the viewpoint that a heat radiating member having better thermal conductivity can be easily obtained. It may be the above.

The reactive compound is preferably a compound having functional groups at both ends of its main chain because it can form a linear bond, and the coupling agent preferably contains oxylanyl or oxetanyl. It is more preferable that the reactive compound has hydroxy from the viewpoint that it can easily react with the group of.

As the reactive compound having hydroxy, a compound represented by the formula (3) or (4) (hereinafter, also referred to as “compound (3)” and “compound (4)”, respectively) is preferable.
Compound (3) means a compound represented by the formula (3), and may mean at least one of the compounds represented by the formula (3). Hereinafter, compounds represented by other formulas are also referred to in the same manner.

In formula (3), R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 3 carbon atoms.

In equation (3), 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, and m + n = 5. Yes, p + q = 5.

In formula (3), A is a single bond, alkylene with 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenanthrene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2, 7-diyl, dodecahydrofluorene-2,7-diyl, bicyclo [2.2.2] octo-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, 4,4' -(9-Fluorene lidene) diphenylene, adamantane diyl, viadamantane diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, or tetradecahydrophenanthrene-2,7-diyl.
In an alkylene having 1 to 10 carbon atoms, at least one hydrogen may be replaced with a halogen.
Cyclohexylene, cyclohexenylene, phenanthrene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, dodecahydrofluorene-2,7-diyl, bicyclo [2.2. 2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, 4,4'-(9-fluorene lidene) diphenylene, adamantane diyl, biadamantandiyl, phenanthrene-2,7 In −diyl, 9,10-dihydrophenanthrene-2,7-diyl, or tetradecahydrophenanthrene-2,7-diyl, at least one −CH ₂ − may be replaced with −O− and at least 1 One -CH = may be replaced with -N =, and at least one hydrogen may be replaced with a halogen, an alkyl having 1 to 10 carbon atoms, or an alkyl halide having 1 to 10 carbon atoms. _{At least one −CH 2} − in an alkyl having 1 to 10 carbon atoms or an alkyl halide having 1 to 10 carbon atoms may be replaced with −O−, −CO−, −COO−, or −OCO−.

The adamantane diyl is generated by removing one hydrogen atom from each of any two ring carbon atoms of adamantane, such as adamantane-1,2-diyl and adamantane-1,3-diyl. A divalent group. Similarly, viadamantane diyl refers to a divalent group formed by removing one hydrogen atom from any two ring carbon atoms of viadamantane.

A in the formula (3) is a single bond, an alkylene having 1 to 10 carbon atoms, a phenylene, or at least one, from the viewpoint of being a compound having desired physical properties and excellent in synthesis and handling. Phenylene in which hydrogen is replaced with halogen or methyl is preferable.
When A contains a compound containing an aromatic ring, it tends to be possible to easily obtain a heat radiating member having better heat resistance and thermal conductivity, and when A contains an alkylene, the reactivity is increased by lowering the melting point of the obtained compound. Can be improved.

In formula (3), Z ¹ and Z ² are independently single bonds or alkylenes having 1 to 22 carbon atoms.
In the alkylene, at least one -CH ₂ − may be replaced with -O-, -S-, -CO-, -COO-, or -OCO-, and at least one hydrogen is replaced with a halogen. May be good.

^{Preferred Z 1} and Z ² are independently single-bonded, − (CH ₂ ) _a −, −O −, −, respectively, from the viewpoints of having desired physical properties and being excellent in synthesis and handling. O (CH ₂ ) _a −, − (CH ₂ ) _a O−, −O (CH ₂ ) _a O−, _{−COO−, −OCO−, −CH 2} CH ₂ −COO−, −OCO−CH ₂ CH _{It is 2-} , -OCF _2- , or -CF ₂ O-, and the a is an integer of 1 to 20.
When Z ¹ and Z ² contain a bond such as alkylene or —O—, the reactivity can be improved by lowering the melting point of the obtained compound.

Examples of particularly preferable compound (3) include compounds (3-1) to (3-11).

^{R 1} , R ² , m, n, p, q, Z ¹ , and Z ² in equations (3-1) to (3-11) are independently synonymous with equation (3), and R ³ to R ⁶³ is independently hydrogen, halogen, an alkyl having 1 to 10 carbon atoms, or an alkyl halide having 1 to 10 carbon atoms. However, − (C (R ³ ) (R ⁴ )) _m − in the formula (3-1) is an alkylene having 1 to 10 carbon atoms or a halogenated alkylene having 1 to 10 carbon atoms.

In equation (4), x is an integer of 2 or more.

In formula (4), ring C is a group obtained by removing at least two hydrogens from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, 9,9-diphenylfluorene, adamantane, and adamantane. ,
In these groups, at least one −CH ₂ − may be replaced by −O−, at least one −CH = may be replaced by −N =, and at least one hydrogen may be a halogen, carbon. It may be replaced with an alkyl having a number of 1 to 3 or an alkyl halide having 1 to 3 carbon atoms, and at least one −CH ₂ − in the alkyl having 1 to 3 carbon atoms or an alkyl halide having 1 to 3 carbon atoms. May be replaced with -O-, -CO-, -COO-, or -OCO-.

The ring C in the formula (4) is a ring selected from benzene, naphthalene, 9,9-diphenylfluorene, or adamantane from the viewpoint of being a compound having desired physical properties and excellent in synthesis and handling. Therefore, it is preferable that the group is obtained by removing at least two hydrogens.

Examples of particularly preferable compound (4) include compounds (4-1) to (4-10).

Each of x in the formulas (4-1) to (4-10) is independently synonymous with the formula (4).
For example, in the above formula (4-7), hydroxy is described only in the lower right ring portion, but the position of hydroxy is not limited to this portion, and even if it is bonded to the lower left ring or the like. It may be bonded to a plurality of rings, and is optional. The same applies to the formulas (4-2) to (4-6) and the formula (4-10).

As the reactive compound having hydroxy, a liquid crystal reactive compound may be used from the viewpoint that a heat radiating member having better thermal conductivity can be obtained.
As the liquid crystal-reactive compound, the liquid crystal compound represented by the formula (5) is preferable. Compound (5) has a liquid crystal skeleton and two or more hydroxy groups, 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 crystal compounds or polymerizable compounds.
The "liquid crystalline compound" refers to a compound that expresses a liquid crystal phase such as a nematic phase or a smectic phase.

By appropriately selecting the rings D, W, and Y of the compound (5), the physical properties such as the liquid crystal phase expression region can be arbitrarily adjusted, and a compound having the desired physical properties can be obtained.

In equation (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.

In the formula (5), Y is independently a single bond or an alkylene having 1 to 20 carbon atoms, preferably an alkylene having 1 to 10 carbon atoms. In these alkylenes having 1 to 20 carbon atoms, at least one -CH _2- that is not bonded to hydroxy is replaced with -O-, -S-, -CO-, -COO-, or -OCO-. Also, at least one hydrogen may be replaced with a halogen.
When Y is a linear alkylene, it tends to be a compound having a wide temperature range of the liquid crystal phase and a low viscosity. On the other hand, when Y is a branched alkylene, the compound tends to have good compatibility with other liquid crystal compounds.

In formula (5), ring D is independently selected from cyclohexane, cyclohexene, benzene, naphthalene, tetrahydronaphthalene, fluorene, bicyclo [2.2.2] octane, and bicyclo [3.1.0] hexane. It is a group from which at least two hydrogens have been removed.
In these groups, at least one −CH ₂ − may be replaced by −O−, at least one −CH = may be replaced by −N =, and at least one hydrogen is cyano, It may be replaced with a halogen, an alkyl having 1 to 10 carbon atoms, or an alkyl halide having 1 to 10 carbon atoms, and in the alkyl (including the alkyl in the alkyl halide), at least one −CH ₂ − is used. It may be replaced by −O−, −CO−, −COO−, −OCO−, −CH = CH−, or −C≡C−.

When at least one of the rings D is 1,4-phenylene, the compound tends to have a large orientation parameter and magnetic anisotropy.
When at least two of the rings D are 1,4-phenylene, the temperature range of the liquid crystal phase is wide and the compound tends to have a high transparency point.
When at least one of the rings D is a group in which at least one hydrogen on the 1,4-phenylene ring is substituted with cyano, halogen, -CF ₃ , or -OCF ₃ , the compound has high dielectric anisotropy. There is a tendency.
Further, when at least one of the rings D is 1,4-cyclohexylene, the compound tends to have a high transparency point and a low viscosity.

Preferred ring D 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-diyl, 9 -Ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7-diyl, 9,9-difluorofluorene-2,7-diyl and the like can be mentioned.

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

More preferable ring D 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 rings D are 1,4-cyclohexylene and 1,4-phenylene. When a compound in which the ring D is such a ring is used, it has a linear structure, so that a heat radiating member having excellent thermal conductivity can be easily obtained.

In formula (5), W is independently a single bond or an alkylene having 1 to 22 carbon atoms.
In the alkylene, at least one −CH ₂₋ is −O−, −S−, −CO−, −COO−, −OCO−, −CH = CH−, −CF = CF−, −CH = N−. , -N = CH-, -N = N-, -N (O) = N-, or -C≡C-, and at least one hydrogen may be replaced with a halogen.

W is a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, or- When (CH ₂ ) ₄ −, in particular, single bond, − (CH ₂ ) ₂ −, −CF ₂ O−, −OCF ₂ −, −CH = CH −, or − (CH ₂ ) ₄ −. In the case, the compound tends to have a low viscosity.
When W is −CH = CH−, −CH = N−, −N = CH−, −N = N−, or −CF = CF−, the compound tends to have a wide temperature range of the liquid crystal phase. In the case of an alkylene having about 4 to 10 carbon atoms, the melting point of the compound tends to decrease.

Preferred Ws are 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.

More preferable Ws are 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 Ws are single bonds, − (CH ₂ ) _2- , −COO−, or −OCO−.

When the compound (5) has three or less rings, the viscosity tends to be low, and when the compound (5) has three or more rings, the transparent point tends to be high. In addition, in this specification, a condensed ring including a 6-membered ring and a 6-membered ring is basically regarded as a ring, and for example, a 3-membered ring, a 4-membered ring, and a 5-membered ring alone are not regarded as a ring. Further, a fused ring such as a naphthalene ring or a fluorene ring is regarded as one ring.

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 may have an axial asymmetry. The molecular configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located in any of the rings D, W, and Y. Having an asymmetric carbon tends to result in a compound having excellent compatibility with other components. When compound (5) has axial chirality, it tends to be a compound having a large twist-inducing force. In addition, the light application property may be any.

Specific examples of more preferable combinations _{of Y and -ring D- (W-ring D) S-} W-ring D- in compound (5) are shown below.

-Method for synthesizing compounds (3) to (5) Compounds (3) to (5) can be synthesized by combining known methods in synthetic organic chemistry. Methods for introducing the desired end groups, rings, and linking groups into the starting material are, for example, 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 Experimental Chemistry Course (Maruzen), etc. It is described in.

[Content of reactive compound]
The amount of the reactive compound used is preferably 1 mol or slightly larger than 1 mol of the target to which the compound binds (eg, coupling agent B in the composite material B2).
The content of the coupling agent and the reactive compound in the present composition is preferably 1.1 to 50 weight by weight from the viewpoint that a heat radiating member having a good balance of high thermal conductivity and high heat resistance can be easily obtained. %, More preferably 2 to 30% by weight.

<Other ingredients>
The present composition further comprises a curing accelerator, an organic compound not bonded to a filler (however, a compound other than a polymer containing a ring having hydroxy), and initiation of polymerization, as long as the effects of the present invention are not impaired. It may contain an agent, a solvent, a stabilizer, an organic filler, and the like.
As each of these other components, one kind may be used, or two or more kinds may be used.

Further, if necessary, the present composition contains a filler to which the coupling agent is not bound, and a coupling agent to a third filler different from the first and second fillers, as long as the effect of the present invention is not impaired. Even if a composite material C1 to which C is bonded, a composite material C2 in which a third filler different from the first and second fillers is bonded to one end of the coupling agent C and a reactive compound is bonded to the other end, is used. Good.
As these fillers, composite material C1 and composite material C2, one kind may be used respectively, or two or more kinds may be used. Examples of these fillers and the third filler include fillers similar to the fillers mentioned as the first and second fillers.
When the composite materials C1 and C2 are not used, anisotropy may occur in the physical properties of the heat radiating member. However, by using the composite materials C1 and C2, the orientation of the filler is relaxed and the anisotropy is reduced. It tends to be easier.

[Curing accelerator]
The present composition is cured in order to promote the reaction between the coupling agent and the polymer, the reaction between the coupling agent and the reactive compound, and specifically, to promote the reaction between oxylanyl or oxetanyl and hydroxy. It is preferable to use an accelerator.
Conventionally known compounds as such a curing accelerator include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite. , Imidazole compounds such as epoxy-imidazole adduct or derivatives thereof, phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium-tetraphenylborate, triphenylphosphonium-triphenylborane, diphenylphosphinyl hydroquinone, 1,8-diaza- Examples thereof include tertiary amines such as bicyclo [5.4.0] -undecene-7, 1,5-diaza-bicyclo [4.3.0] -nonen-5, or tertiary amine salts thereof.

[Organic compounds not bound to filler]
Examples of the organic compound not bonded to the filler include polymerizable compounds, non-polymerizable compounds, polymer compounds, etc., and are polymerizable compounds (hereinafter, also referred to as “unbound polymerizable compounds”) and non-polymerizable compounds. Liquid crystal compounds, polymer compounds and the like are preferable.
The organic compound that is not bonded to the filler means an organic component that is not bonded to the filler when blended in the present composition, and may be bonded to the filler in the heat radiating member. ..
As the particle size of the filler is increased, the porosity in the heat radiating member may increase, but by using an organic compound that is not bound to the filler, the porosity can be reduced, resulting in thermal conductivity and water vapor. There is a tendency that a heat radiating member having excellent breaking performance can be easily obtained.

Regarding the amount of the organic compound not bonded to the filler, first, a heat radiating member is prepared without using the compound, and if a void exists in the obtained heat radiating member, the amount of the void is measured and the void is determined. It is desirable that the amount be filled.

-Unbonded polymerizable compound The unbonded polymerizable compound is not particularly limited, and may be a compound similar to the compound listed in the column of the reactive compound forming the composite material B2, and has a liquid crystal property. It may be a non-existent compound or a compound having liquidity. The unbonded polymerizable compound may be monofunctional or bifunctional or higher.
As the unbonded polymerizable compound, a compound that does not reduce the moldability and mechanical strength of the present composition is preferable, and examples of the compound include an epoxy resin.
Examples of the polymerizable compound having no liquid crystal property include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives and the like.

-Non-polymerizable liquid crystal compounds The non-polymerizable liquid crystal compounds are not particularly limited, but compounds described in LiqCryst, LCI Publisher GmbH, Hamburg, Germany, etc., which are databases of liquid crystal compounds, etc. Can be mentioned. Among these, a compound having a property of not flowing in the temperature range in which the heat radiating member is used is preferable.
By polymerizing the composition containing the non-polymerizable liquid crystal compound, for example, a composite material of the liquid crystal compound and a polymer of the reactive compound forming the composite material B2 can be obtained. In one aspect of this composite material, a non-polymerizable liquid crystal compound can be present in the polymer network, such as a polymer dispersed liquid crystal.

When the non-polymerizable liquid crystal compound is used, the non-polymerizable liquid crystal compound may be injected into the generated voids in a temperature range showing an isotropic phase after the present composition is cured. , The present composition containing a non-polymerizable liquid crystal compound may be polymerized.

-Polymer compound The polymer compound may be a compound other than the polymer containing a ring having hydroxy, but a compound that does not reduce the moldability and mechanical strength of the present composition is preferable. The polymer compound is preferably a polymer compound that does not react with the composite material, and specific examples thereof include polyolefin-based resins, polyvinyl-based resins, polyamide-based resins, and polyitaconic acid-based resins.

[Polymerization initiator]
The polymerization initiator may be appropriately selected depending on the type of the unbonded polymerizable compound and the like, and specific examples thereof include a photoradical polymerization initiator, a photocationic polymerization initiator, and a thermal polymerization initiator. , Thermal polymerization initiator is preferable.
The thermal polymerization initiator is preferably benzoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butyl peroxide (DTBP). ), T-Butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN) and the like.

[solvent]
When it is necessary to polymerize the present composition, the polymerization may be carried out in a solvent or in the absence of a solvent. In the former case or when the composition is applied onto a substrate or the like, the composition may contain a solvent.
The solvent is preferably benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopenta. Non, cyclohexanone, propylene glycol methyl ether acetate (PGMEA) and the like can be mentioned.
The amount of the solvent used is not particularly limited, and may be determined for each individual case in consideration of polymerization efficiency, solvent cost, energy cost, and the like.

[Stabilizer]
By using the stabilizer, the handling of the present composition tends to be easier.
As the stabilizer, known stabilizers can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT).

≪Manufacturing method of composition≫
The method for producing the present composition (hereinafter, also referred to as “the present method”) includes a step a of combining the first filler and the coupling agent A to obtain the composite material A1 and a step a of obtaining the composite material A1 obtained in the step a. , And step c1 of mixing the polymer containing a ring having hydroxy.

Further, in this method, the step a of combining the first filler and the coupling agent A to obtain the composite material A1 and
Step b1 of combining the second filler and the coupling agent B to obtain the composite material B1, or
The second filler and one end of the coupling agent B are bonded, and then the other end of the coupling agent B is bonded to the reactive compound, or one end of the coupling agent B and the reactive compound are bonded. Then, the other end of the coupling agent B is bonded to the second filler to obtain the composite material B2, and the step b2.
Including the step c2 of mixing the composite material A1 obtained in the step a, the composite material B1 obtained in the step b1 or the composite material B2 obtained in the step b2, and the polymer containing a ring having a hydroxy. Good.

-Step of binding the filler and the coupling agent The step of binding the filler and the coupling agent is not particularly limited, and a known method can be used. By this step, composite materials A1 and B1 and the like can be obtained.

The following method is preferable as the step of binding the filler and the coupling agent.
The filler and the coupling agent are mixed in the presence of a solvent, stirred with a stirrer or the like, and then dried. After the solvent is dried, it is held under vacuum conditions using a vacuum dryer or the like. If necessary, a purification step may be carried out in which a solvent is added after the holding, and the coupling agent adhering (not bound) to the solid content is released and removed by ultrasonic treatment, centrifugation or the like. .. This purification step may be performed a plurality of times. Further, the purified composite material may be dried using an oven or the like.

The solvent is not particularly limited, but it is preferably a solvent in which the coupling agent can be dissolved, and a solvent in which the filler can be dispersed is preferable.
The time for mixing and stirring the filler and the coupling agent is not particularly limited, and examples thereof include 1 minute to 24 hours.

The drying conditions (eg, drying time, drying temperature, drying atmosphere) are not particularly limited as long as the solvent used is dried, and may be appropriately set according to the solvent used.
When holding under the vacuum conditions or the like, the holding temperature is preferably 20 to 250 ° C., and the holding time is 1 minute to 24 hours.

-Step of binding the coupling agent and the reactive compound The step of binding the coupling agent (including the coupling agent bonded to the filler) and the reactive compound is not particularly limited, and a known method should be used. Can be done. When a coupling agent bonded to the filler is used in this step, a composite material B2 or the like can be obtained.

The following method is preferable as the step of binding the coupling agent and the reactive compound.
The coupling agent and the reactive compound are mixed using an agate mortar, a mixer or the like, and then kneaded using a biaxial roll or the like. Then, if necessary, separation and purification (removal of the reactive compound not bound to the coupling agent) is performed by ultrasonic treatment, centrifugation or the like.

-Mixing step The mixing step (steps c1 and c2) is not particularly limited, and examples thereof include the following methods.
In steps c1 and c2, the amount of filler in the obtained heat radiating member is weighed within the above range, and in step c2, the mixing ratio of the first filler and the second filler is further within the following range. Weigh and mix in an agate mortar. Then, the mixture is mixed using a twin-screw roll or the like.

The mixing ratio of the first filler and the second filler may be determined according to the number of reactive groups as the reaction points of each component so that the desired reaction sufficiently occurs, but specifically. Is preferably 1: 0.01 to 1:30, more preferably 1: 0.1 to 1:10 in terms of weight ratio.

≪Heat dissipation member≫
The heat radiating member according to the embodiment of the present invention (hereinafter, also referred to as "the present heat radiating member") is obtained by curing the present composition.
This heat radiating member is excellent in high thermal conductivity and high heat resistance in a well-balanced manner, and is excellent in chemical stability, hardness, mechanical strength and the like. The mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, flexural modulus, impact strength, and the like.
This heat dissipation member is suitable for a heat dissipation substrate, a heat dissipation plate (plane heat sink), a heat dissipation sheet, a heat dissipation film, a heat dissipation coating film, a heat dissipation adhesive, a heat dissipation molded product, and the like.

The shape, size, thickness, etc. of the heat radiating member are not particularly limited, and may be appropriately selected according to a desired application.
Examples of the shape of the heat radiating member include a plate-like body such as a sheet, a film, and a thin film, a molded body (eg, a housing) according to a desired application, and the like.
The thickness of the heat radiating member is 2 μm or more, preferably 5 μm to 10 cm, more preferably 10 μm to 1 cm, and particularly preferably 20 μm to 1 mm. The thickness may be appropriately changed according to the intended use.

The thermal conductivity of the heat radiating member can be evaluated by the thermal conductivity in the thickness direction thereof.
The vertical thermal conductivity of this heat radiating member is preferably 2.2 W / (m · K) or more, more preferably 5 W / (, from the viewpoint of excellent thermal conductivity and being suitable for use as a heat radiating plate or the like. m · K) or more, particularly preferably 8 W / (m · K) or more.
Specifically, the thermal conductivity can be measured by the method described in Examples.

The heat resistance of the heat radiating member can be evaluated by measuring the 5% weight loss temperature.
The 5% weight reduction temperature of the heat radiating member is preferably 280 ° C. or higher, more preferably 300 ° C. or higher, particularly preferably 300 ° C. or higher, because it has excellent heat resistance and can be suitably used for heat radiating members for high power. It is 320 ° C. or higher.
The 5% weight loss temperature can be specifically measured by the method described in Examples.

The coefficient of thermal expansion of the heat radiation member can be evaluated by the coefficient of elongation in the plane direction (the direction substantially perpendicular to the film thickness direction) in the range of 50 to 200 ° C.
The coefficient of thermal expansion of the heat radiating member is preferably -20 to 50 ppm / K, more preferably -5 to 20 ppm / K, because it is difficult to thermally expand and can be suitably used for a die attachment to a metal substrate that generates heat. It is K.
Specifically, the coefficient of thermal expansion can be measured by the method described in Examples.

The hygroscopicity of the heat radiating member is preferably 1.5% or less from the viewpoint of low hygroscopicity and suitable use for the substrate material in the package.
Specifically, the hygroscopicity can be measured by the method described in Examples.

[Manufacturing method of heat dissipation member]
The heat radiating member can be obtained by curing the composition, and may be molded if necessary.

The curing method is not particularly limited, and is not particularly limited as long as the present composition is cured, but thermosetting is preferable.
The temperature at the time of the curing is, for example, room temperature to 350 ° C., preferably room temperature to 250 ° C., more preferably 50 to 200 ° C., and the curing time is, for example, 5 seconds to 50 hours, preferably 1 minute to 30 hours. , More preferably 5 minutes to 20 hours.
After curing by applying heat, it is preferable to slowly cool it in order to suppress stress strain and the like. Further, heating may be performed twice or more to relax stress strain and the like.

The following method is preferable as a method for producing the film-shaped heat radiating member.
The composition is sandwiched between predetermined plates, heated and pressed using a compression molding machine, and oriented and cured by compression molding. Further, post-curing is performed using an oven or the like.
Examples of the heating temperature and the post-curing temperature include the same temperature as the curing temperature, and the pressure at the time of pressurization is basically preferably high, and specifically preferably. Is 1 to 300 MPa, more preferably 10 to 300 MPa.

As a method for producing a film-shaped heat radiating member, in addition to the above-mentioned method, the following method using the present composition containing a solvent is also preferable.
After applying this composition containing a solvent to a substrate or the like, the solvent is removed and then polymerization is carried out by light or heat. After that, it is heated to an appropriate temperature and post-treated by thermosetting.

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, and meniscus coating.

The solvent can be removed by drying, for example, by air-drying at room temperature, drying on a hot plate or a drying oven, or blowing hot air or hot air.
The conditions for removing the solvent are not particularly limited, and the coating film may be dried until the solvent is generally removed and the coating film loses its fluidity.

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, and nitride. Inorganic insulating substrate such as aluminum; polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene Examples thereof include resin substrates such as naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose or a partially saponified product thereof, epoxy resin, phenol resin, and norbornene resin.

The resin substrate may be an unstretched film, a uniaxially stretched film, or a biaxially stretched film.
The resin substrate may be subjected to surface treatment such as saponification treatment, corona treatment, and plasma treatment in advance. Further, a protective layer may be provided on these resin substrates so as not to be attacked by the solvent that can be contained in the present composition. Examples of the material used as the protective layer include polyvinyl alcohol. Further, an anchor coat layer may be provided in order to improve the adhesion between the protective layer and the substrate. Such an anchor coat layer may be either an inorganic material layer or an organic material layer as long as it is a layer that enhances the adhesion between the protective layer and the substrate.

≪Electronic equipment≫
An electronic device according to an embodiment of the present invention is an electronic device including the heat radiating member and an electronic device having a heat generating portion, and arranged in the electronic device so that the heat radiating member comes into contact with the heat generating portion. ..
According to such an electronic device, the heat generated in the electronic device can be efficiently dissipated by the heat radiating member having high thermal conductivity.

Examples of the electronic device include a semiconductor element. In particular, an insulated gate bipolar transistor (IGBT), which requires a more efficient heat dissipation mechanism due to its high power among semiconductor elements, is a preferable example. 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 and the like.
Examples of electronic devices equipped with IGBTs include uninterruptible power supplies, variable voltage variable frequency control devices for AC motors, railroad vehicle control devices, electric transport devices such as hybrid cars and electric cars, and IH cookers.

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 materials used in the following examples are as follows.

<Filler>
-"Boron Nitride Particles": h-BN particles, manufactured by Momentive Performance Materials Japan (same as above), PolarTherm PTX-25 (trade name)

<Silane coupling agent>
-"Sila Ace S510": trade name, 3-glycidoxypropyltrimethoxysilane, manufactured by JNC Co., Ltd.- "Sila Ace S320": trade name, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, Made by JNC Co., Ltd.

<Polymer containing a ring having hydroxy>
・ "Marukalinker S-2P": trade name, polyparavinylphenol, manufactured by Maruzen Petrochemical Co., Ltd. ・ "Marukalinker CMM": trade name, 4-vinylphenol / methyl methacrylate copolymer, Maruzen Petrochemical Co., Ltd. ) ・ "SP1010": Product name, Novolac type phenol resin, manufactured by Asahi Organic Materials Industry Co., Ltd.

<Reactive compound>
-"Bisphenol A": 4,4'-(propane-2,2-diyl) diphenol, manufactured by Wako Pure Chemical Industries, Ltd.

<Polymer without a ring having hydroxy>
・ "JER807": Product name, epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd. ・ "jER828": Product name, epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.

<Curing accelerator>
-"Curing accelerator": 2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.

[Synthesis Example 1] Preparation of Composite Material A1 1.5 g of Syrah Ace S510 was added to 150 mL of pure water, and the mixture was stirred at 500 rpm for 15 hours using a stirrer. Next, 15 g of boron nitride particles were added to the solution after stirring for 15 hours, and the mixture was stirred at 500 rpm for 1 hour using a stirrer, the obtained mixture was dried at 50 ° C. for 5 hours, and further, a vacuum oven set at 80 ° C. Was heat-treated for 5 hours under vacuum conditions.
The obtained particles are used as the composite material A1.

[Synthesis Example 2] Preparation of Composite Material A2 15 g of boron nitride particles and 2.25 g of Sila Ace S320 were added to 150 mL of toluene, and the mixture was stirred at 500 rpm for 1 hour using a stirrer. The obtained mixture was dried at 40 ° C. for 6 hours, and further heat-treated under vacuum conditions for 5 hours using a vacuum oven set at 120 ° C.
The obtained particles are used as the composite material A2.

[Synthetic Example 3] Preparation of Composite Material B Weigh 1 2 g of composite material A, 3.96 g of bisphenol A, and 40 mg of a curing accelerator, and roll two rolls of these (IMC-AE00 type, manufactured by Imoto Seisakusho Co., Ltd.). Was mixed at 160 ° C. for 10 minutes. The weight ratio at the time of this mixing is an amount in which the number of hydroxys in the composite material A1 with respect to oxylanyl is doubled or more, and an amount in which each of the above components can be sufficiently kneaded on two rolls. ..

The obtained mixture is added to 45 mL of tetrahydrofuran, and after sufficient stirring, the insoluble matter is precipitated by a centrifuge (manufactured by Hitachi Koki Co., Ltd., high-speed cooling centrifuge CR22N type, 4,000 rpm × 10 minutes × 25 ° C.). And the solution containing unreacted bisphenol A was removed by decantation (hereinafter, also referred to as "cleaning step"). Subsequently, the same operation as in the above-mentioned washing step was carried out on the obtained precipitate except that 45 mL of acetone was used instead of 45 mL of tetrahydrofuran. Further, the above-mentioned washing step using tetrahydrofuran and acetone in order was repeated.
Composite material B was obtained by drying the sediment after a series of washing steps. The composite material B was a particle in which sila ace S510 was bonded to the boron nitride particles and bisphenol A was further bonded to the sila ace S510.

<Content of organic matter in composite material>
The composite material obtained in Synthesis Examples 1 to 3 was heated to 900 ° C. using a thermogravimetric / differential thermal measuring device (TG-8121, manufactured by Rigaku Co., Ltd.). The amount of heat reduction at this time was defined as the amount of the organic component (eg, silane coupling agent, reactive compound) bonded to the boron nitride particles in the composite materials obtained in Synthesis Examples 1 to 3. The results are shown in Table 1.

[Example 1]
A composition was obtained by mixing 639 mg of composite material A1, 61 mg of Marcalinker S-2P, and 18 μL of a solution of 10 mg of a curing accelerator in 2 mL of acetone. The obtained composition was sandwiched between two stainless steel plates so that the thickness of the obtained heat radiating member was about 600 μm, and the two plates were set at 170 ° C., a compression molding machine (Imoto Seisakusho Co., Ltd.). , IMC-19EC) was used to pressurize to 30 MPa, and the heating state was continued for 10 minutes to perform orientation treatment and pre-curing. Since the boron nitride particles are plate-like particles, when the composition spreads between the stainless steel plates, the particles are oriented so that the plane direction of the particles is parallel to the surface of the stainless steel plate.
After cooling, the sample removed from the two stainless steel plates was cured after 15 hours under vacuum conditions using a vacuum oven (manufactured by Yamato Scientific Co., Ltd., DP300) set at 170 ° C. to obtain a heat dissipation member. It was.

[Example 2]
A composition and a heat radiating member were prepared in the same manner as in Example 1 except that the amounts of the composite material A1 and the Marca Linker S-2P used were changed to 588 mg of the composite material A1 and 112 mg of the Marca Linker S-2P, respectively.

[Example 3]
A composition and a heat radiating member were produced in the same manner as in Example 2 except that the Marcalinker CMM was used instead of the Marcalinker S-2P.

[Example 4]
The composition was prepared in the same manner as in Example 2 except that SP1010 was used as the raw material of the composition, except that SP1010 was used, and the pre-curing temperature was 130 ° C. and the post-curing temperature was 150 ° C. A heat-dissipating member was produced by curing the composition obtained in the same manner as in Example 2 except for the above.

[Example 5]
Composition and heat dissipation member in the same manner as in Example 1 except that composite material A1 439 mg, composite material B 247 mg, and composite material S-2P 14 mg were used instead of composite material A1 639 mg and Marca Linker S-2P 61 mg. Was produced.

[Example 6]
The composition was the same as in Example 5, except that the amounts of the composite material A1, the composite material B, and the Marcalinker S-2P were changed to 528 mg of the composite material A1, 86 mg of the composite material B, and 86 mg of the Marcalinker S-2P, respectively. An object and a heat radiating member were manufactured.

[Example 7]
A composition and a heat radiating member were prepared in the same manner as in Example 1 except that composite material A1 596 mg, Marcalinker S-2P 47 mg, and jER807 57 mg were used instead of composite material A1 639 mg and Marca Linker S-2P 61 mg. did.

[Comparative Example 1]
The composition and heat radiating member were prepared in the same manner as in Example 1 except that boron nitride particles 619 mg, Marca Linker S-2P 61 mg, and Sila Ace S510 20 mg were used instead of the composite material A1 639 mg and Marca Linker S-2P 61 mg. Made.

[Comparative Example 2]
A composition and a heat radiating member were prepared in the same manner as in Example 4, except that boron nitride particles 569 mg, SP1010 112 mg, and Sila Ace S510 19 mg were used instead of the composite material A1 588 mg and SP1010 112 mg.

[Comparative Example 3]
A composition and a heat radiating member were prepared in the same manner as in Example 1 except that boron nitride particles 581 mg, Marcalinker S-2P 61 mg, and jER807 58 mg were used instead of the composite material A1 639 mg and Marca Linker S-2P 61 mg. did.

[Comparative Example 4]
With the same composition as in Example 1, except that 577 mg of boron nitride particles, 47 mg of Marcalinker S-2P, 57 mg of jER807, and 19 mg of Sila Ace S510 were used instead of 639 mg of composite material A1 and 61 mg of Marcalinker S-2P. A heat radiating member was produced.

[Comparative Example 5]
A composition and a heat radiating member were prepared in the same manner as in Example 1 except that boron nitride particles 581 mg, Marcalinker S-2P 61 mg, and jER828 58 mg were used instead of the composite material A1 639 mg and Marca Linker S-2P 61 mg. did.

[Comparative Example 6]
The composition was prepared in the same manner as in Example 1 except that the raw materials of the composition were changed to 588 mg of composite material A2 and 112 mg of jER828, and the pre-curing temperature was 150 ° C. and the post-curing temperature was 150 ° C. , The composition obtained in the same manner as in Example 1 was cured to prepare a heat radiating member.

[Reference example 1]
The composition and the heat radiating member were prepared in the same manner as in Example 1 except that the raw materials of the composition were changed to 329 mg of composite material A1 and 371 mg of composite material B.

<Content of organic matter in heat dissipation member>
The organic content in the heat radiating member was measured in the same manner as the organic content in the composite material except that the heat radiating members obtained in Examples and Comparative Examples were used instead of the composite material. .. The results are shown in Table 2.

<5% weight loss temperature>
The 5% weight reduction temperature of the heat radiating member obtained in Examples and Comparative Examples is a heating temperature of 140 to 900 ° C. when the heat radiating member is heated to 900 ° C. using the same device as for measuring the organic content. The amount of weight loss was 100% by weight, and the temperature when the weight was reduced by 5% by weight from the weight of the heat radiating member at 140 ° C. was measured. The results are shown in Table 2.

<Hygroscopicity>
The heat radiating members obtained in Examples and Comparative Examples were dried under vacuum conditions for 2 hours using a vacuum oven set at 150 ° C. _{The weight (W 0} g) of the heat radiating member after drying was measured. Next, _{the weight (W 1 ) when the heat radiating member after measuring the weight W 0} was held in a constant temperature and humidity chamber (manufactured by ESPEC Co., Ltd., LHL-113) at 85 ° C. and 85 RH% for 42 hours and then taken out. g) was measured, and the moisture absorption rate of the heat radiating member was calculated by the following formula. The results are shown in Table 2.
Hygroscopicity (%) = (W ₁ − W ₀ ) × 100 / W ₀

<Thermal conductivity>
The thermal conductivity is determined in advance by the specific heat of the heat dissipation member (measured by Rigaku Co., Ltd., DSC type high-sensitivity differential scanning calorimeter Thermo Plus EVO2 DSC-8231) and the specific gravity (manufactured by Shinko Denshi Co., Ltd., electronic scale type specific gravity). (Measured by a total DME-220), and by multiplying that value by the thermal diffusivity obtained by the ai-Phase Mobile 1u thermal diffusivity measuring device manufactured by iPhase Co., Ltd., the heat dissipation member The thermal conductivity in the thickness direction was determined. The results are shown in Table 2.

<Coefficient of thermal expansion>
A test piece having a width of 4 mm was cut out from the heat radiating member obtained in Examples and Comparative Examples, and tested in the process of raising the temperature from 50 ° C. to 250 ° C. using a TMA-SS6100 thermomechanical analyzer manufactured by SII Co., Ltd. The change in the length of the piece was measured. The coefficient of thermal expansion (ppm / K) at 50 to 200 ° C. was determined from the rate of change in the length of the test piece (ppm) based on the length of the test piece at 50 ° C. In the evaluation of the dimensional change, the above measurement was repeated twice. Specifically, the heat radiating member obtained above was heated to 250 ° C. (first time), cooled to 50 ° C., and heated to 250 ° C. again (second time). Table 2 shows the calculation results of the coefficient of thermal expansion at 50 to 200 ° C. Further, the thermal expansion behavior of the heat radiating member obtained in each test example at 50 to 250 ° C. (temperature dependence of the rate of change in the length of the test piece) is shown in FIGS. 1 to 14, respectively.

Comparing Example 1 and Comparative Example 1, Example 1 in which the composite material A1 was prepared in advance with the filler and the coupling agent had thermal conductivity and heat resistance as compared with Comparative Example 1 in which the composite material was not formed. The property (5% weight loss temperature) was improved. In Example 1, the fillers were covalently bonded to each other via a coupling agent and a polymer to facilitate heat transfer and improve heat resistance, whereas in Comparative Example 1, the coupling agent was used. It is considered that the formation of covalent bonds via the polymer was only partial. Similarly, in Example 4, the thermal conductivity and heat resistance are improved as compared with Comparative Example 2 in which the composite material is not formed. Further, Example 7 has higher thermal conductivity and heat resistance than Comparative Example 3 in which the coupling agent is not used and Comparative Example 4 in which the composite material of the coupling agent and the filler is not formed.

In Example 5 using the composite material A1, the composite material B, and the Marcalinker S-2P as materials, heat resistance, low hygroscopicity, and thermal conductivity are compared with Reference Example 1 using only the composite material A1 and the composite material B. Both are excellent in sex. In Example 6 in which the ratio of Marcalinker S-2P was increased, the heat resistance and thermal conductivity were improved as compared with Example 5, although the hygroscopicity was slightly increased.

Further, while Examples 1 to 7 all showed a 5% weight loss temperature of 315 ° C. or higher and a thermal conductivity of 8.5 W / m · K or higher, an amino-based coupling agent was used. Comparative Example 6 prepared by using the composite material A2 and the epoxy-based polymer was inferior in heat resistance, moisture absorption rate, and thermal conductivity as compared with Examples. In the examples, it is considered that the fillers can be covalently bonded to each other using a composite material via a coupling agent and a polymer. At this time, a coupling agent having oxylanyl and a polymer containing a ring having hydroxy are included. Is considered to be particularly effective in improving the material properties.

As shown in Table 2 and FIGS. 1 to 7, the coefficient of thermal expansion of Examples 1 to 7 is about 10 ppm / K from the negative coefficient of thermal expansion, so that the difference in coefficient of thermal expansion from other members is small. , It is possible to manufacture a heat radiating member having an appropriate coefficient of thermal expansion according to the application.

In view of the above results, it can be seen that the heat radiating member is a heat conductive material having high heat resistance.

Claims (16)

Composite material A1 in which the coupling agent A is bonded to the first filler, and
A composition comprising a polymer containing a ring having a hydroxy. Composite material B1 in which the coupling agent B is bonded to the second filler, and
Composite material B2 in which a second filler is bonded to one end of the coupling agent B and a reactive compound is bonded to the other end.
The composition according to claim 1, further comprising at least one selected from. The composition according to claim 1 or 2, wherein the polymer is a polymer having at least one of the structures represented by the formulas (1) and (2):

In equation (1), m has an average value of 2 to 100;
n is independently greater than or equal to 1 on average;
R ¹ is independently alkylene, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octo-1 having 1 to 10 carbon atoms. , 4-diyl, bicyclo [3.1.0] hex-3,6-diyl, or 4,4'-(9-fluorenelilidene) diphenylene.
In the alkylene with 1 to 10 carbon atoms, at least one hydrogen may be replaced with _{-CH 3 or hydroxy.}
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octo-1,4-diyl, bicyclo [3.1.0] hex In −3,6-diyl, and 4,4'-(9-fluorenelilidene) diphenylene, at least one −CH ₂ − may be replaced by −O−, and at least one −CH = is −N. It may be replaced with =, and at least one hydrogen may be replaced with hydroxy, halogen, an alkyl having 1 to 10 carbon atoms, or an alkyl halide having 1 to 10 carbon atoms, and the hydrogen having 1 to 10 carbon atoms. _{At least one −CH 2} − in an alkyl or an alkyl halide having 1 to 10 carbon atoms may be replaced with −O−, −CO−, −COO−, or −OCO−;
Ring A is a group from which at least two hydrogens have been removed from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, and 9,9-diphenylfluorene.
In these groups, at least one -CH = may be replaced with -N = and at least one hydrogen is a halogen, an alkyl having 1-3 carbon atoms, or an alkyl halide having 1-3 carbon atoms. _{May be replaced, at least one −CH 2} − in the alkyl having 1-3 carbon atoms or the alkyl halide having 1-3 carbon atoms is −O−, −CO−, −COO−, or −OCO−. May be replaced by;

In equation (2), m has an average value of 2 to 100;
n is independently greater than or equal to 1 on average;
Ring B is an independent group from which at least three hydrogens have been removed from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, and 9,9-diphenylfluorene.
In these groups, at least one -CH = may be replaced with -N = and at least one hydrogen is a halogen, an alkyl having 1-3 carbon atoms, or an alkyl halide having 1-3 carbon atoms. _{May be replaced, at least one −CH 2} − in the alkyl having 1-3 carbon atoms or the alkyl halide having 1-3 carbon atoms is −O−, −CO−, −COO−, or −OCO−. May be replaced by;
R ² and R ⁴ are independently single bonds or alkylenes having 1 to 5 carbon atoms.
In the alkylene, at least one −CH ₂ − may be replaced by −O−, −S−, −CO−, −COO−, or −OCO−, and at least one hydrogen is −CH ₃ or −. May be replaced by OH;
R ³ is independently single-bonded, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, 1,1'-biphenyl-4,4'-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] Oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, or 4,4'-(9-fluorenelilidene) diphenylene.
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, 1,1'-biphenyl-4,4'diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Oct-1, In 4-diyl, bicyclo [3.1.0] hex-3,6-diyl, and 4,4'-(9-fluorenelilidene) diphenylene, at least one -CH ₂ -is replaced by -O-. Also, at least one -CH = may be replaced with -N =, and at least one hydrogen is hydroxy, halogen, alkyl having 1 to 10 carbon atoms, or alkyl halide having 1 to 10 carbon atoms. _{It may be replaced by at least one −CH 2} − in the alkyl having 1 to 10 carbon atoms or the alkyl halide having 1 to 10 carbon atoms being −O−, −CO−, −COO−, or −OCO−. May be replaced with. The composition according to any one of claims 1 to 3, wherein the polymer is a polymer having a hydroxy bonded to an aromatic ring in the side chain. In the above formula (1)
R ¹ is independently an alkylene, cyclohexylene, cyclohexenylene, phenylene, or naphthalene-2,6-diyl having 1 to 10 carbon atoms.
Ring A is a group that independently removes at least two hydrogens from benzene or naphthalene.
The composition according to claim 3. In the above formula (2)
Ring B is independently a group of benzene or naphthalene from which at least three hydrogens have been removed.
R ³ is independently a single bond, cyclohexylene, phenylene, naphthalene-2,6-diyl, or 1,1'-biphenyl-4,4'diyl,
The composition according to claim 3. The composition according to any one of claims 1 to 6, wherein the polymer contains a structure derived from a ring-free monomer having at least one hydroxy selected from a (meth) acrylic compound and a vinyl compound. The composition according to any one of claims 1 to 7, wherein the filler is an inorganic filler selected from oxides, nitrides, carbides, and carbon materials. The filler is at least one selected from alumina, silica, titania, zirconia, cordierite, boron nitride, boron carbide, boron nitride carbon, graphite, carbon fibers, carbon nanotubes, and graphene, claims 1 to 8. The composition according to any one of the above. The composition according to any one of claims 1 to 9, wherein the coupling agent contains oxylanyl or oxetanyl. The composition according to any one of claims 1 to 10, which comprises an organic compound which is not bonded to the filler (however, it is a compound other than a polymer containing a ring having a hydroxy). The composition according to any one of claims 1 to 11, which is for a heat radiating member. A heat radiating member obtained by curing the composition according to any one of claims 1 to 12. The heat radiating member according to claim 13 and an electronic device having a heat generating portion are provided.
An electronic device arranged in the electronic device so that the heat radiating member comes into contact with the heat generating portion. Step a of combining the first filler and the coupling agent A to obtain the composite material A1 and
A method for producing a composition, which comprises the composite material A1 obtained in the step a and the step c1 in which a polymer containing a ring having a hydroxy is mixed. Step a of combining the first filler and the coupling agent A to obtain the composite material A1 and
Step b1 of combining the second filler and the coupling agent B to obtain the composite material B1, or
The second filler and one end of the coupling agent B are bonded, and then the other end of the coupling agent B is bonded to the reactive compound, or one end of the coupling agent B and the reactive compound are bonded. Then, the other end of the coupling agent B is bonded to the second filler to obtain the composite material B2, and the step b2.
A step c2 of mixing the composite material A1 obtained in step a, the composite material B1 obtained in step b1 or the composite material B2 obtained in step b2, and a polymer containing a ring having a hydroxy is included. Method for producing composition.

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