WO2019188973A1 - Composition, heat dissipation member, electronic device and method for producing composition - Google Patents

Abstract

One embodiment of the present invention relates to a composition, a heat dissipation member, an electronic device, and a method for producing a composition; and the composition contains a composite material A1, which is obtained by binding a coupling agent A to a first filler, and a polymer that comprises a ring having a hydroxy group.

Description

Composition, heat dissipation member, electronic device, and method for producing composition

Embodiments of the present invention relate to a composition, a heat dissipation member, an electronic device, and a method for manufacturing the composition.

In recent years, in semiconductor elements for power control, such as hybrid cars and electric cars, and CPUs for high-speed computers, the temperature of internal semiconductors has been increased and heat conduction has been increased so that the temperature of internal semiconductors does not become too high. The ability to effectively release (dissipate) heat to the outside has become important.

As an example of the heat dissipation method, there is a method in which a high heat conductive material (heat dissipation member) is brought into contact with the heat generating portion to guide heat to the outside and dissipate heat. Examples of such high thermal conductivity materials include metal materials such as metals and inorganic materials such as metal oxides, but these inorganic materials have problems in workability and ease of cracking and are useful as heat dissipation materials. There is no such thing.

In order to solve these problems, a heat radiating member in which a resin and an inorganic material are mixed to achieve high thermal conductivity has been developed. For example, Patent Document 1 discloses a phenol resin molding material containing a phenol resin and boron nitride at a predetermined ratio.

JP 2006-096858 A

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

In addition, due to recent downsizing, higher integration, higher power, etc., the heat radiating member is required to have high heat dissipation and high reliability. Specifically, a predetermined effect even at high temperatures. Therefore, heat resistance is required for high reliability.

One embodiment of the present invention provides a heat dissipating member excellent in balance between high thermal conductivity and high heat resistance, and a composition capable of forming the heat dissipating member.

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

[1] A composite material A1 in which a coupling agent A is bonded to a first filler;
And a polymer comprising a ring having hydroxy.

[2] Composite material B1 in which coupling agent B is bound to the second filler, and
Composite material B2 in which the second filler is bonded to one end of coupling agent B and the 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 structures represented by formulas (1) and (2).

[In the formula (1), m is an average value of 2 to 100;
n is independently an average value of 1 or more;
R ¹ is independently alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-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-fluorenylidene) diphenylene,
In alkylene having 1 to 10 carbon atoms, at least one hydrogen may be replaced by —CH ₃ or hydroxy,
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, bicyclo [3.1.0] hex In —3,6-diyl and 4,4 ′-(9-fluorenylidene) diphenylene, at least one —CH ₂ — may be replaced by —O—, and at least one —CH═ is —N And at least one hydrogen may be replaced by hydroxy, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons, and having 1 to 10 carbons In the alkyl or the halogenated alkyl having 1 to 10 carbon atoms, at least one —CH ₂ — is substituted with —O—, —CO—, —COO—, or —OCO—. May be replaced;
Ring A is a group in which at least two hydrogens are 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 by —N═, and at least one hydrogen is a halogen, an alkyl having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. In the alkyl having 1 to 3 carbon atoms or the halogenated alkyl having 1 to 3 carbon atoms, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. May be replaced. ]

[In the formula (2), m is an average value of 2 to 100;
n is independently an average value of 1 or more;
Ring B is independently a group in 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 by —N═, and at least one hydrogen is a halogen, an alkyl having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. In the alkyl having 1 to 3 carbon atoms or the halogenated alkyl having 1 to 3 carbon atoms, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. May be replaced by;
R ² and R ⁴ are each independently a single bond or alkylene 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 a single bond, 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-fluorenylidene) 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-fluorenylidene) diphenylene, at least one —CH ₂ — is replaced by —O—. And at least one —CH═ may be replaced by —N═, and the at least one hydrogen is hydroxy, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons. may be replaced, at least one -CH in halogenated alkyl alkyl or C 1 -C 10 carbon number 1-10 ₂ -, -O -, - CO , It may be replaced by -COO-, or -OCO-. ]

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

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

[6] In the formula (2),
Ring B is independently a group obtained by removing at least three hydrogens from benzene or naphthalene,
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 includes a structure derived from a monomer that does not include a ring having at least one hydroxy group 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, boron nitride carbon, graphite, carbon fiber, carbon nanotube, and graphene. ] To [8].

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

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

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

[14] A heat radiating member according to [13] and an electronic device having a heat generating part,
An electronic apparatus disposed in the electronic device such that the heat dissipation member is in contact with the heat generating portion.

[15] A step of obtaining the composite material A1 by combining the first filler and the coupling agent A;
A method for producing a composition, comprising: composite A1 obtained in step a; and step c1 in which a polymer containing a hydroxy-containing ring is mixed.

[16] A step of obtaining a composite material A1 by combining the first filler and the coupling agent A;
A step b1 of obtaining a composite material B1 by bonding the second filler and the coupling agent B, or
By binding the second filler and one end of the coupling agent B and then binding the other end of the coupling agent B to the reactive compound, or binding one end of the coupling agent B and the reactive compound And then b2 to obtain the composite material B2 by bonding the other end of the coupling agent B to the second filler,
Including 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 step c2 of mixing a polymer containing a ring having a hydroxy group. A method for producing the composition.

According to one embodiment of the present invention, it is possible to provide a heat dissipating member that is excellent in balance between high thermal conductivity and high heat resistance. Furthermore, it is possible to provide a heat dissipating member that is excellent in 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. FIG. 2 is a graph showing the thermal expansion behavior of the heat dissipating member manufactured in Example 2. FIG. 3 is a graph showing the thermal expansion behavior of the heat dissipating member manufactured in Example 3. 4 is a graph showing the thermal expansion behavior of the heat dissipating member manufactured in Example 4. FIG. 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 dissipation member manufactured in Comparative Example 2. FIG. 10 is a graph showing the thermal expansion behavior of the heat dissipating member manufactured in Comparative Example 3. FIG. 11 is a graph showing the thermal expansion behavior of the heat dissipation member manufactured in Comparative Example 4. FIG. 12 is a graph showing the thermal expansion behavior of the heat dissipation 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 dissipating member manufactured in Reference Example 1.

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

≪Composition≫
A composition according to an embodiment of the present invention (hereinafter also referred to as “the present composition”) includes a composite material A1 in which a coupling agent A is bonded to a first filler, a polymer including a ring having hydroxy, including.
Since the present composition is characterized by including a composite material in which a filler and a coupling agent or the like are bonded in advance, the composition does not include such a composite material, and the filler and the coupling agent are simply mixed. The effects described above are different from those of the composition prepared in (1).

In an embodiment in which the present composition is cured, the fillers are coupled with a coupling agent and a polymer (herein, the coupling agent and the polymer are reacted with a reactive group (eg, oxiranyl or hydroxy). The same applies to the following.), Or a heat dissipation member including a complex three-dimensionally bonded via a coupling agent and a polymer and / or a reactive compound. A heat dissipation member including such a composite is considered to exhibit high thermal conductivity not only in the horizontal direction but also in the thickness direction.

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

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

<Filler>
It does not restrict | limit especially as a 1st and 2nd filler, An inorganic filler or an organic filler may be sufficient, and a conventionally well-known filler can be used.
The first and second fillers may be different fillers, but for the sake of clarity, only the “first” and “second” are attached, and therefore the same filler may be used.

Examples of the filler include alumina, magnesia, beryllia, silica, titania, zirconia, zinc oxide, cordierite, copper oxide, cerium oxide, yttrium oxide, tin oxide, holmium oxide, bismuth oxide, cobalt oxide, and calcium oxide. Materials: nitrides such as boron nitride, aluminum nitride, silicon nitride, boron nitride carbon; carbides such as boron carbide and silicon carbide; carbon materials such as diamond, graphite, carbon fiber, carbon nanotube, 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 fibers and carbon fibers, and cloths thereof ; Polyvinylformer , Polyvinyl butyral, polyesters, polyamides, organic fillers, and the like, such as fibers or particles made of polyimide.
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, for example, alumina, silica, titania, zirconia, cordierite, boron nitride, boron carbide, boron nitride carbon, graphite, carbon, in terms of thermal conductivity, availability, and coupling agent coupling. Fibers, carbon nanotubes, and graphene are preferred.
Moreover, when these fillers are used, it is possible to easily obtain a heat radiating member having a high thermal conductivity and a very low or negative thermal expansion coefficient.

This composition preferably contains a highly thermally conductive inorganic filler. Examples of the high thermal conductivity inorganic filler include boron nitride, aluminum nitride, silicon nitride, boron nitride carbon, boron carbide, silicon carbide, diamond, graphite, carbon fiber, carbon nanotube, beryllia, magnesia, alumina, and the like.

As the first and second fillers, boron nitride, boron carbide, boron nitride carbon, graphite, carbon fiber, carbon nanotube, and graphene are preferable. 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. In particular, h-BN has a low dielectric constant, It is preferable because of its high insulation. For example, it is preferable to use a plate-like filler such as h-BN or graphite because the plate-like structure can be oriented along a mold or the like during molding or curing.

The type, shape, size, and the like of the filler can be appropriately selected according to the purpose. 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 cylindrical shape. .

The average particle size of the filler is preferably from 0.1 to 500 μm, more preferably from 1 to 200 μm, from the viewpoint that a heat radiating member excellent in thermal conductivity can be easily obtained.
In addition, the average particle diameter in this specification is a median diameter based on the particle size distribution measurement by a laser diffraction / scattering method. In addition, the average particle diameter refers to the average value of the length of the long side when the filler shape is a plate shape, and in the case of a fiber shape or a rod shape, the average value of the fiber length or the length of the rod. That means.

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

<Coupling agent>
The coupling agent (coupling agent A or B) used in the present composition is a compound having at least two reactive groups and capable of binding to a filler. The coupling agent is preferably a compound capable of reacting with hydroxy.
Coupling agents A and B may be different coupling agents, but for the sake of clarity, only “A”, “B”, etc. are attached, so that the same coupling agent may be used. Good.

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

Since the coupling agent used in the present composition binds to the filler, it preferably contains a hydrolyzable group such as alkoxy capable of binding.
Further, the coupling agent used in the present composition preferably reacts with hydroxy, and further preferably does not react with hydroxy to form a highly polar amide bond or urethane bond, so oxiranyl or oxetanyl, particularly It is preferred to have oxiranyl.
The coupling agent used in the present 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 oxiranyl or oxetanyl include Silaace (trade names) S510 and S530 manufactured by JNC Corporation.

Since the reaction amount of the coupling agent with respect to the filler varies mainly depending on the size of the filler and the reactivity of the coupling agent to be used, it is difficult to define.
It is preferable to bind as many coupling agents as possible to the filler, so that the number of reactive groups reacting with the reactive group of the coupling agent is the same or slightly larger than the number of reactive groups of the filler. It is preferable to use a coupling agent.
The amount of coupling agent bonded to 100 parts by weight of the filler is preferably 1 to 30 parts by weight, more preferably 2 parts, from the viewpoint that a heat radiating member excellent in balance between high thermal conductivity and high heat resistance can be easily obtained. -25 parts by weight, more preferably 3-20 parts by weight.

<Polymer>
The composition includes a polymer comprising a ring having a hydroxy. By using such a polymer, it is possible to easily obtain a heat radiating member excellent in balance between high thermal conductivity and high heat resistance.
The hydroxy may be directly bonded to the ring or may be bonded via a predetermined linking group, but the above effect is more exerted, and a heat radiating member having particularly excellent thermal conductivity can be easily obtained. From the viewpoint of being able to do so, it is preferable that it is directly bonded to the ring.
In addition, the ring is preferably an aromatic ring (including a heteroaromatic ring) from the viewpoint that the above-described effect is more exhibited and a heat dissipation member that is particularly excellent in heat resistance can be easily obtained. The polymer is particularly preferably a polymer having hydroxy (phenolic hydroxy) bonded to an aromatic ring in the side chain.
In addition, the polymer in this specification refers to the compound which has 2 or more of repeating units (for example, the structure repeated m pieces in Formula (1)).
In the present composition, one type of polymer may be used, or two or more types of polymers may be used.

The polymer is not particularly limited as long as it includes a ring having a hydroxy group. However, from the viewpoint of easily obtaining a heat radiating member excellent in balance due to high thermal conductivity and high heat resistance, the polymer (1) or (2 It is preferable that it is a polymer containing the structure represented by this.
The polymer may include a polymer including both the structure represented by Formula (1) and the structure represented by Formula (2), or may include a polymer including either one of them.

The content of the structure represented by the formulas (1) and (2) in the polymer is 100% by weight of the polymer in terms of easily obtaining a heat radiating member having better thermal conductivity and heat resistance. On the other hand, it is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.

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

The “average value of m” refers to an average value of a portion corresponding to m in a case where the polymer may exist with a certain distribution. The same description in this specification shows the same meaning.
“N is independently” means that when m is 2 or more, there are two or more n in formula (1). In this case, two or more n may be the same or different. Means good. The same description in this specification shows the same meaning.
In addition, in a certain formula in this specification, when two or more identical codes exist, when two or more identical codes exist in different formulas, groups represented by these codes may be the same or different. Good.

In the formula (1), R ¹ is independently alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-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-fluorenylidene) diphenylene,
In alkylene having 1 to 10 carbon atoms, at least one hydrogen may be replaced by —CH ₃ or hydroxy,
Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, bicyclo [3.1.0] hex In —3,6-diyl and 4,4 ′-(9-fluorenylidene) diphenylene, at least one —CH ₂ — may be replaced by —O—, and at least one —CH═ is —N And at least one hydrogen may be replaced by hydroxy, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons, and having 1 to 10 carbons In the alkyl or the halogenated alkyl having 1 to 10 carbon atoms, at least one —CH ₂ — is substituted with —O—, —CO—, —COO—, or —OCO—. It may be replaced.

The term “at least one” means “at least one selected without distinction”, but usually a structure that is difficult to adopt based on common sense in this field, for example, —O— in which oxygen and oxygen are adjacent to each other. It is preferable not to contain O-.

R ¹ is independently preferably an alkylene, cyclohexylene, or cyclohexenylene having 1 to 10 carbon atoms from the standpoint that a heat dissipation member having excellent flexibility can be easily obtained. R ¹ is independently preferably phenylene or naphthalene-2,6-diyl from the standpoint 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 by —N═, and at least one hydrogen is a halogen, an alkyl having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. In the alkyl having 1 to 3 carbon atoms or the halogenated alkyl having 1 to 3 carbon atoms, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. May be replaced.
Among these, the ring A is preferably independently a group in which at least two hydrogens are removed from benzene or naphthalene, from the viewpoint that a heat radiating member having higher heat resistance can be easily obtained. More preferably it is a group excluding at least two, preferably two hydrogens.

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

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

Ring B is independently a group in 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 by —N═, and at least one hydrogen is a halogen, an alkyl having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. In the alkyl having 1 to 3 carbon atoms or the halogenated alkyl having 1 to 3 carbon atoms, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. May be replaced.
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. More preferred is a group excluding at least three, preferably three hydrogens.

R ² and R ⁴ are each independently a single bond or alkylene 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 with OH.
Increasing the number of carbon atoms in the alkylene makes it easier to obtain a heat-dissipating member with excellent flexibility, while the thermal conductivity tends to decrease. Therefore, R ² and R ⁴ are each independently a single bond or an alkylene having 1 to 5 carbon atoms. Are preferably combined appropriately.

R ³ is independently a single bond, 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-fluorenylidene) 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-fluorenylidene) diphenylene, at least one —CH ₂ — is replaced by —O—. And at least one —CH═ may be replaced by —N═, and the at least one hydrogen is hydroxy, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons. may be replaced, at least one -CH in halogenated alkyl alkyl or C 1 -C 10 carbon number 1-10 ₂ -, -O -, - CO , It may be replaced by -COO-, or -OCO-.

From the standpoint of improving the heat resistance and thermal conductivity of the resulting heat dissipation member, R ³ is independently a single bond, cyclohexylene, phenylene, naphthalene-2,6-diyl, or 1,1′-biphenyl-4,4. 'Diyl is preferable, and a single bond, phenylene, or naphthalene-2,6-diyl is more preferable.

A polymer containing a 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. 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 include a hydroxy-containing ring.
The monomer that does not contain a ring having hydroxy may be a monofunctional compound or a bifunctional or higher compound. For example, (meth) acrylic compounds such as (meth) acrylic acid alkyl esters, ethylene, propylene, styrene, acetic acid And vinyl compounds such as vinyl.
In addition, it is a ring which has a hydroxy that the monomer which does not contain the ring which has the said hydroxy does not contain, and this monomer may contain the ring which is not couple | bonded with the ring and does not have a hydroxy.

When the polymer contains a structure derived from a monomer that does not contain a ring having hydroxy, it does not contain a ring having hydroxy in the polymer from the viewpoint of easily obtaining a heat dissipation member that is superior in heat resistance. The content of the monomer-derived structure 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 that does not contain a ring having a hydroxy group can be synthesized by a conventionally known method, for example, a compound that induces a structure represented by the formula (1) or (2) such as vinylphenol is polymerized. In this case, polymerization may be performed using a monomer that does not contain a ring having hydroxy, and after synthesizing a compound having a structure represented by formula (1) or (2), the compound and a ring having hydroxy are formed. You may superpose | polymerize with the monomer which does not contain.

Commercially available products may be used as the polymer, and examples of the polymer having a structure represented by the formula (1) include polyvinylphenol resins (such as Maruka Linker series manufactured by Maruzen Petrochemical Co., Ltd.). Examples of the polymer having the structure represented by the formula (2) include conventionally known phenol resins such as phenol novolac resins, alkylphenol novolac resins, resol resins, and cresol novolac resins.

The content of the polymer in the composition is preferably 0.1 to 49% by weight, more preferably from the viewpoint that a heat radiating member excellent in balance between 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 that can be combined with the coupling agent and can form the composite material B2.
1 type may be sufficient as the reactive compound used for this composition, and 2 or more types may be sufficient as it.

The reactive compound used as a raw material for the composite material B2 is preferably a bifunctional or higher functional compound from the viewpoint of easily obtaining a heat radiating member that is superior in thermal conductivity. It may be the above.

The reactive compound is preferably a compound having a functional group at both ends of the main chain because it can form a linear bond, and the coupling agent preferably contains oxiranyl or oxetanyl. From the standpoint of being able to easily react with the group, a reactive compound having hydroxy is more preferable.

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)”) is preferable.
The compound (3) means a compound represented by the formula (3), and may mean at least one compound represented by the formula (3). Hereinafter, compounds represented by other formulas have the same notation.

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

In the formula (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 the formula (3), A represents a single bond, alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2, 7-diyl, dodecahydrofluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl, 4,4 ′ -(9-fluorenylidene) diphenylene, adamantanediyl, biadamantanediyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, or tetradecahydrophenanthrene-2,7-diyl;
In the alkylene having 1 to 10 carbon atoms, at least one hydrogen may be replaced with a halogen,
Cyclohexylene, cyclohexenylene, phenylene, 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-fluorenylidene) diphenylene, adamantanediyl, biadamantanediyl, phenanthrene-2,7 In -diyl, 9,10-dihydrophenanthrene-2,7-diyl, or tetradecahydrophenanthrene-2,7-diyl, at least one —CH ₂ — may be replaced by —O— and at least 1 -CH = may be replaced by -N =, where at least one hydrogen is halogen, carbon The alkyl having 1 to 10 carbon atoms or the alkyl halide having 1 to 10 carbon atoms may be substituted, and at least one —CH ₂ — in the alkyl having 1 to 10 carbon atoms or the halogenated alkyl having 1 to 10 carbon atoms may be substituted. May be replaced by —O—, —CO—, —COO—, or —OCO—.

Adamantanediyl is produced by removing one hydrogen atom from any two ring carbon atoms of adamantane such as adamantane-1,2-diyl, adamantane-1,3-diyl, and the like. Refers to a divalent group. Similarly, biadamantanediyl refers to a divalent group generated by removing one hydrogen atom from any two ring carbon atoms of biadamantane.

A in formula (3) is a single bond, alkylene having 1 to 10 carbon atoms, phenylene, or at least one compound because the compound has desired physical properties and is easy to synthesize and handle. Preference is given to phenylene in which hydrogen is replaced by halogen or methyl.
When a compound containing an aromatic ring is used as A, there is a tendency that a heat radiating member that is superior in heat resistance and thermal conductivity tends to be obtained. When A contains alkylene, reactivity is reduced by lowering the melting point of the obtained compound. Can be improved.

In formula (3), Z ¹ and Z ² are each independently a single bond or alkylene 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. Also good.

Desirable Z ¹ and Z ² are each independently a single bond, — (CH ₂ ) _a —, —O—, — from the viewpoint of having a desired physical property, being a compound that is easy to synthesize and easy to handle. O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O—, —COO—, —OCO—, —CH ₂ CH ₂ —COO—, —OCO—CH ₂ CH ₂ —, —OCF ₂ —, or —CF ₂ O—, and 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 resulting compound.

Particularly preferred examples of compound (3) include compounds (3-1) to (3-11).

R ¹ , R ² , m, n, p, q, Z ¹ , and Z ² in formulas (3-1) to (3-11) are each independently synonymous with formula (3), and R ³ to Each R ⁶³ is independently hydrogen, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons. In the formula (3-1), — (C (R ³ ) (R ⁴ )) _m — represents an alkylene having 1 to 10 carbon atoms or a halogenated alkylene having 1 to 10 carbon atoms.

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

In formula (4), ring C is a group in which at least two hydrogens have been removed from a ring selected from benzene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, 9,9-diphenylfluorene, adamantane, and biadamantane. ,
In these groups, at least one —CH ₂ — may be replaced with —O—, at least one —CH═ may be replaced with —N═, and at least one hydrogen may be halogen, carbon It may be substituted with an alkyl having 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 the alkyl halide having 1 to 3 carbon atoms may be substituted. May be replaced by —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 that the compound has desired physical properties and is easy to synthesize and handle. From the above, a group in which at least two hydrogen atoms are removed is preferable.

Particularly preferred examples of the compound (4) include compounds (4-1) to (4-10).

In the formulas (4-1) to (4-10), each x is independently synonymous with the formula (4).
For example, in the 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 may be 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 formulas (4-2) to (4-6) and formula (4-10).

As the hydroxy-containing reactive compound, a liquid crystalline reactive compound may be used from the viewpoint that a heat radiating member having better thermal conductivity can be obtained.
As the liquid crystalline reactive compound, a liquid crystal compound represented by the formula (5) is preferable. The 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 crystalline compounds or polymerizable compounds.
The “liquid crystalline compound” refers to a compound that exhibits 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 the formula (5), s is an integer of 0 to 4, t is an integer of 1 or more, and u is an integer of 1 or more.

In formula (5), each Y is independently a single bond or alkylene having 1 to 20 carbon atoms, preferably alkylene having 1 to 10 carbon atoms. In these alkylene groups having 1 to 20 carbon atoms, at least one —CH ₂ — not bonded to hydroxy is replaced with —O—, —S—, —CO—, —COO—, or —OCO—. Alternatively, 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 liquid crystal phase temperature range and a low viscosity. On the other hand, when Y is branched alkylene, it tends to be a compound having good compatibility with other liquid crystal compounds.

In formula (5), each ring D is independently a ring selected from cyclohexane, cyclohexene, benzene, naphthalene, tetrahydronaphthalene, fluorene, bicyclo [2.2.2] octane, and bicyclo [3.1.0] hexane. From which at least two hydrogens are removed,
In these groups, at least one —CH ₂ — may be replaced with —O—, at least one —CH═ may be replaced with —N═, and at least one hydrogen is cyano, It may be replaced by halogen, alkyl having 1 to 10 carbon atoms, or alkyl halide having 1 to 10 carbon atoms, and in the alkyl (including alkyl in the halogenated alkyl), at least one —CH ₂ — is 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, it tends to be a compound having a large orientational order parameter and magnetization anisotropy.
When at least two of the rings D are 1,4-phenylene, the liquid crystal phase has a wide temperature range and tends to be a compound having a high clearing 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 a high dielectric anisotropy. There is a tendency.
Further, when at least one of the rings D is 1,4-cyclohexylene, it tends to be a compound having a high clearing point and a low viscosity.

Preferred ring D includes 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, - diyl, 9-ethyl-2,7-diyl, 9-fluoro-2,7-diyl, 9,9-difluoro-2,7-diyl, and the like.

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

More 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, a linear structure is obtained, so that a heat radiating member having excellent thermal conductivity can be easily obtained.

In formula (5), each W is independently a single bond or 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 — In the case of (CH ₂ ) ₄ —, in particular, a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, or — (CH ₂ ) ₄ —. In the case, it tends to be a compound having a low viscosity.
When W is —CH═CH—, —CH═N—, —N═CH—, —N═N—, or —CF═CF—, the liquid crystal phase tends to have a wide temperature range. In the case of alkylene having 4 to 10 carbon atoms, the melting point of the compound tends to decrease.

Preferred W is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, — OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — ( CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— and the like.

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

When the compound (5) has 3 or less rings, the viscosity is low, and when it has 3 or more rings, the clearing point tends to be high. In the present specification, basically, a 6-membered ring and a condensed ring including a 6-membered ring are regarded as a ring, and for example, a 3-membered ring, a 4-membered ring, and a 5-membered ring alone are not regarded as a ring. A condensed 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 an axial asymmetry. The configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located in any of rings D, W, and Y. When it has asymmetric carbon, it tends to be a compound having excellent compatibility with other components. When the compound (5) has axial asymmetry, 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.

Synthesis method of compounds (3) to (5) Compounds (3) to (5) can be synthesized by combining known methods in organic synthetic chemistry. Methods for introducing the desired end groups, rings, and linking groups into the starting material include, for example, Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Books such as Wily & Sons, Inc., Organic Reactions, John Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen) It is described in.

[Reactive compound content]
It is preferable to use the reactive compound so that the amount of the reactive compound is 1 mol or slightly more than 1 mol of the target to which the compound is bonded (eg, coupling agent B in the composite material B2).
The content of the coupling agent and the reactive compound in the composition is preferably 1.1 to 50% by weight from the viewpoint that a heat radiating member excellent in balance between high thermal conductivity and high heat resistance can be easily obtained. %, More preferably 2 to 30% by weight.

<Other ingredients>
This composition is an organic compound not bonded to a curing accelerator and filler (however, it is a compound other than a polymer containing a ring having a hydroxy), and polymerization initiation, as long as the effects of the present invention are not impaired. Agents, solvents, stabilizers, organic fillers and the like may be included.
Each of these other components may be used alone or in combination of two or more.

In addition, in the present composition, the coupling agent is added to a third filler different from the first filler and the second filler, which are not bound to the coupling agent, as long as the effects of the present invention are not impaired. Even if a composite material C1 in 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 may be used. Good.
Each of these fillers, composite material C1, and composite material C2 may be used alone or in combination of two or more. Examples of the filler and the third filler include fillers similar to the fillers mentioned as the first and second fillers.
When composite materials C1 and C2 are not used, anisotropy may occur in the physical properties of the heat dissipation member. However, by using composite materials C1 and C2, the orientation of the filler is relaxed and the anisotropy is reduced. It tends to be easier.

[Curing accelerator]
In order to promote the reaction between the coupling agent and the polymer, the reaction between the coupling agent and the reactive compound, and the like, specifically, the composition is cured to promote the reaction between oxiranyl or oxetanyl and hydroxy. It is preferable to use an accelerator.
Examples of such curing accelerators include conventionally known compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Imidazole compounds such as epoxy-imidazole adducts or derivatives thereof, phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium-tetraphenylborate, triphenylphosphonium-triphenylborane, diphenylphosphinylhydroquinone, 1,8-diaza- And tertiary amines such as bicyclo [5.4.0] -undecene-7,1,5-diaza-bicyclo [4.3.0] -nonene-5 or tertiary amine salts thereof.

[Organic compounds not bound to filler]
Examples of the organic compound not bonded to the filler include a polymerizable compound, a non-polymerizable compound, a polymer compound, and the like. A polymerizable compound (hereinafter also referred to as “unbonded polymerizable compound”), a non-polymerizable compound. A liquid crystal compound, a polymer compound and the like are preferable.
The organic compound that is not bonded to the filler refers to an organic component that is not bonded to the filler when blended in the composition, and may be bonded to the filler in the heat dissipation member. .
As the particle size of the filler is increased, the void ratio in the heat dissipation member may increase. However, by using an organic compound that is not bonded to the filler, the void can be reduced, and thermal conductivity and water vapor can be reduced. There exists a tendency which can obtain easily the heat radiating member which is excellent by interruption | blocking performance.

The amount of the organic compound not bonded to the filler is as follows. First, when a heat radiating member is prepared without using the compound, and there is a void in the obtained heat radiating member, the amount of the void is measured, It is desirable that the amount be filled.

Unbonded polymerizable compound The unbonded polymerizable compound is not particularly limited, and may be the same compound as the compound listed in the column of the reactive compound forming the composite material B2, and has liquid crystallinity. Or a compound having liquid crystallinity. The unbonded polymerizable compound may be monofunctional or bifunctional or more.
The unbonded polymerizable compound is preferably a compound that does not reduce the moldability and mechanical strength of the composition, and examples of the compound include an epoxy resin.
Examples of the polymerizable compound having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, and itaconic acid derivatives.

・ Non-polymerizable liquid crystal compound The non-polymerizable liquid crystal compound is not particularly limited, but is a compound described in a list of liquid crystal compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany), etc. Is mentioned. Among these, the compound which has the characteristic which does not flow in the temperature range where a 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 a reactive compound forming the composite material B2 can be obtained. In one embodiment of this composite material, a non-polymerizable liquid crystal compound can be present in the polymer network, such as a polymer-dispersed liquid crystal.

In the case of using the non-polymerizable liquid crystal compound, after curing the composition, the non-polymerizable liquid crystal compound may be injected into the generated void in a temperature range showing an isotropic phase. The present composition containing a non-polymerizable liquid crystal compound may be polymerized.

-High molecular compound Although the said high molecular compound should just be compounds other than the polymer containing the ring which has the said hydroxy, the compound which does not reduce the moldability and mechanical strength of this 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 resins, polyvinyl resins, polyamide resins, and polyitaconic acid resins.

[Polymerization initiator]
The polymerization initiator may be appropriately selected according to the type of the unbonded polymerizable compound, and specific examples thereof include a photo radical polymerization initiator, a photo cationic polymerization initiator, and a thermal polymerization initiator. A thermal polymerization initiator is preferred.
The thermal polymerization initiator is preferably benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBP). ), T-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN) and the like.

[solvent]
When the composition needs to be polymerized, the polymerization may be performed in a solvent or without a solvent. In the former case or when the present composition is applied onto a substrate or the like, the present 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), etc. are mentioned.
The amount of 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 composition tends to be easier to handle.
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).

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

In addition, the method includes the step a of combining the first filler and the coupling agent A to obtain the composite material A1,
A step b1 of obtaining a composite material B1 by bonding the second filler and the coupling agent B, or
By binding the second filler and one end of the coupling agent B and then binding the other end of the coupling agent B to the reactive compound, or binding one end of the coupling agent B and the reactive compound And then b2 to obtain the composite material B2 by bonding the other end of the coupling agent B to the second filler,
Including 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 step c2 of mixing a polymer containing a hydroxy-containing ring. Good.

-The process of combining a filler and a coupling agent It does not restrict | limit especially as a process of combining the said filler and a coupling agent, A well-known method can be used. By this step, the composite materials A1 and B1 can be obtained.

As the step of bonding the filler and the coupling agent, the following method is preferable.
The filler and the coupling agent are mixed in the presence of a solvent, stirred using a stirrer or the like, and then dried. After the solvent is dried, it is kept under a vacuum condition using a vacuum dryer or the like. If necessary, a purification step may be performed to release and remove the coupling agent adhering to solid content (not bound) by adding a solvent after the holding, sonication, centrifugation, etc. . This purification step may be performed a plurality of times. Further, the purified composite material may be dried using an oven or the like.

Although it does not restrict | limit especially as said solvent, It is preferable that it is a solvent which can melt | dissolve a coupling agent, and it is preferable that it is a solvent which can disperse | distribute a filler.
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 to be used is dried, and may be appropriately set according to the solvent to be used.
The holding temperature at the time of holding under the vacuum condition is preferably 20 to 250 ° C., and the holding time is 1 minute to 24 hours.

The step of binding the coupling agent and the reactive compound The step of binding the coupling agent (including the coupling agent bound to the filler) and the reactive compound is not particularly limited, and a known method is used. Can do. In this step, when a coupling agent combined with a filler is used, a composite material B2 or the like can be obtained.

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

-Mixing process Although it does not restrict | limit especially as said mixing process (process c1 and c2), For example, the following method is mentioned.
In steps c1 and c2, the amount of filler in the obtained heat radiating member is weighed so as to be in the above range, and in step c2, the mixing ratio of the first filler and the second filler is further in the following range. Weigh out and mix with agate mortar. Then, it mixes using a biaxial roll etc.

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

≪Heat dissipation material≫
A heat radiating member according to an 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 balance with high thermal conductivity and high heat resistance, and excellent in chemical stability, hardness, mechanical strength, and the like. The mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength, and the like.
This heat radiating member is suitable for a heat radiating substrate, a heat radiating plate (planar heat sink), a heat radiating sheet, a heat radiating film, a heat radiating coating film, a heat radiating adhesive, a heat radiating molded product, and the like.

The shape, size, thickness and the like 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, and a molded body (eg, a housing) according to a desired application.
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. What is necessary is just to change thickness suitably according to a use.

The thermal conductivity of the heat dissipation member can be evaluated by the thermal conductivity in the thickness direction.
The thermal conductivity in the vertical direction of the heat radiating member is preferably 2.2 W / (m · K) or more, more preferably 5 W / (from the viewpoint that it has excellent thermal conductivity and can be suitably used for a heat radiating plate. 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 dissipating member can be evaluated by measuring a 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, and particularly preferably, from the viewpoint that it has excellent heat resistance and can be suitably used for a heat radiating member for high power. 320 ° C. or higher.
The 5% weight loss temperature can be specifically measured by the method described in Examples.

The thermal expansion coefficient of the heat radiating member can be evaluated by the elongation ratio in the plane direction (approximately perpendicular to the film thickness direction) in the range of 50 to 200 ° C.
The thermal expansion coefficient of the heat dissipating member is preferably −20 to 50 ppm / K, more preferably −5 to 20 ppm / K from the viewpoint that it is difficult to thermally expand and can be suitably used for die attachment to a metal substrate that generates heat. K.
The coefficient of thermal expansion can be specifically measured by the method described in the examples.

The moisture absorption rate of the heat dissipating member is preferably 1.5% or less from the viewpoint that it has low hygroscopicity and can be suitably used as a substrate material in a package.
The moisture absorption rate can be specifically measured by the method described in Examples.

[Method of manufacturing 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. Thermal curing is preferable.
The curing temperature 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, it is 5 minutes to 20 hours.
After curing by applying heat, it is preferable to cool slowly to suppress stress strain and the like. Further, heating may be performed twice or more to relieve stress strain and the like.

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

As a method for producing a film-like heat radiation member, in addition to the above-described method, the following method using the present composition containing a solvent is also preferable.
After this composition containing a solvent is applied to a substrate or the like, the solvent is removed, and then polymerization is performed by light or heat. Then, it heats to suitable temperature and performs a post-process 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 in a hot plate or a drying furnace, or blowing hot air or hot air.
The conditions for removing the solvent are not particularly limited, and it may be dried until the solvent is almost removed and the fluidity of the coating film is lost.

Examples of the substrate include metal substrates such as copper, aluminum, and iron; inorganic semiconductor substrates such as silicon, silicon nitride, gallium nitride, and zinc oxide; glass substrates such as alkali glass, borosilicate glass, and flint glass; alumina, and nitride. Inorganic insulating substrates such as aluminum; polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene Naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, tria Chill cellulose or partially saponified product thereof, epoxy resins, phenolic resins, and resin substrate such as a 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, or plasma treatment in advance. Moreover, you may provide the protective layer which is not attacked by the solvent which can be contained in this composition on these resin-made board | substrates. Examples of the material used as the protective layer include polyvinyl alcohol. Furthermore, an anchor coat layer may be provided in order to improve the adhesion between the protective layer and the substrate. As long as such an anchor coat layer is a layer that improves the adhesion between the protective layer and the substrate, it may be an inorganic or organic material layer.

≪Electronic equipment≫
An electronic apparatus according to an embodiment of the present invention is an electronic apparatus that includes the heat dissipating member and an electronic device having a heat generating part, and is disposed in the electronic device so that the heat dissipating member contacts the heat generating part. .
According to such an electronic apparatus, heat generated in the electronic device can be efficiently radiated 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) that requires a more efficient heat dissipation mechanism due to high power among semiconductor elements is a suitable example. An IGBT is one of semiconductor elements and is a bipolar transistor in which a MOSFET is incorporated in a gate portion, and is used for power control applications and the like.
Examples of the electronic device provided with the IGBT include an uninterruptible power supply, an AC motor variable voltage variable frequency control device, a railway vehicle control device, an electric transportation device such as a hybrid car and an electric car, and an IH cooker.

Hereinafter, the present invention will be described in detail using 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), PolarTherm PTX-25 (trade name)

<Silane coupling agent>
“Syra Ace S510”: trade name, 3-glycidoxypropyltrimethoxysilane, manufactured by JNC Corporation “Syra Ace S320”: trade name, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, Made by JNC Corporation

<Polymer including ring having hydroxy>
"Marcalinker S-2P": trade name, polyparavinylphenol, manufactured by Maruzen Petrochemical Co., Ltd. "Marcalinker CMM": trade name, 4-vinylphenol / methyl methacrylate copolymer, Maruzen Petrochemical Co., Ltd. • “SP1010”: trade name, novolac type phenolic resin, manufactured by Asahi Organic Materials Co., Ltd.

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

<Polymer not containing ring having hydroxy>
"JER807": trade name, epoxy resin, manufactured by Mitsubishi Chemical Corporation "jER828": trade name, epoxy resin, manufactured by Mitsubishi Chemical Corporation

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

[Synthesis Example 1] Production of Composite Material A1 1.5 g of Sailer Ace S510 was added to 150 mL of pure water, and stirred for 15 hours at 500 rpm using a stirrer. Next, 15 g of boron nitride particles were added to the solution after stirring for 15 hours, stirred at 500 rpm for 1 hour using a stirrer, the resulting 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 referred to as composite material A1.

[Synthesis Example 2] Production of Composite Material A2 15 g of boron nitride particles and 2.25 g of Silaace 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 subjected to heat treatment under vacuum conditions for 5 hours using a vacuum oven set at 120 ° C.
Let the obtained particle | grains be composite material A2.

[Synthesis Example 3] Preparation of composite material B 2 g of composite material A, 3.96 g of bisphenol A, and 40 mg of a curing accelerator were weighed and two rolls (IMC-AE00, manufactured by Imoto Seisakusho Co., Ltd.) For 10 minutes at 160 ° C. The weight ratio at the time of mixing is such an amount that the number of hydroxys relative to oxiranyl contained in the composite material A1 is twice or more, and is an amount capable of sufficiently kneading the respective components on two rolls. .

The resulting mixture was added to 45 mL of tetrahydrofuran, and after sufficient stirring, the insoluble matter was settled with a centrifuge (Hitachi Koki Co., Ltd., high-speed cooling centrifuge CR22N type, 4,000 rpm × 10 min × 25 ° C.). The solution containing unreacted bisphenol A was removed by decantation (hereinafter also referred to as “cleaning step”). Then, operation similar to the above-mentioned washing | cleaning process was performed with respect to the obtained sediment except having used 45 mL of acetone instead of 45 mL of tetrahydrofuran. Further, the above-described washing process using tetrahydrofuran and acetone in order was repeated.
The composite material B was obtained by drying the sediment after a series of washing processes. The composite B was particles in which Silaace S510 was bonded to the boron nitride particles, and bisphenol A was further bonded to the Silaace S510.

<Content of organic component in composite material>
The composite materials obtained in Synthesis Examples 1 to 3 were heated to 900 ° C. using a thermogravimetric / differential heat measuring apparatus (TG-8121, manufactured by Rigaku Corporation). The amount of decrease in heating at this time was defined as the amount of organic components (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 the composite material A, 61 mg of Marcalinker S-2P, and 18 μL of a solution of 10 mg of the curing accelerator in 2 mL of acetone. A compression molding machine (Imoto Seisakusho Co., Ltd.) in which the obtained composition was sandwiched between two stainless steel plates so that the thickness of the resulting heat dissipation member was about 600 μm, and the two plates were set at 170 ° C. The pressure was increased to 30 MPa using IMC-19EC) and the heating state was continued for 10 minutes to perform alignment treatment and pre-curing. Since the boron nitride particles are plate-like particles, when the composition spreads between the stainless steel plates, the surface direction of the particles and the stainless steel plate surface were oriented in parallel.
After cooling, the sample removed from the two stainless steel plates was post-cured under vacuum conditions for 15 hours using a vacuum oven (manufactured by Yamato Scientific Co., Ltd., DP300) set at 170 ° C. to obtain a heat radiating member. It was.

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

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

[Example 4]
A composition was prepared in the same manner as in Example 2 except that SP1010 was used in place of Marcalinker S-2P as a raw material for the composition. Except for this, the composition obtained in the same manner as in Example 2 was cured to produce a heat dissipation member.

[Example 5]
The composition and heat dissipation member were the same as in Example 1 except that 439 mg of composite material A1, 247 mg of composite material B, and 14 mg of markalinker S-2P were used instead of 639 mg of composite material A1 and 61 mg of Marcalinker S-2P. Was made.

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

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

[Comparative Example 1]
A composition and a heat dissipation member were prepared in the same manner as in Example 1 except that 619 mg of boron nitride particles, 61 mg of Marcalinker S-2P, and 20 mg of Silaace S510 were used instead of 639 mg of Composite A1 and 61 mg of Marcalinker S-2P. Produced.

[Comparative Example 2]
A composition and a heat radiating member were produced in the same manner as in Example 4 except that 589 mg of boron nitride particles, 112 mg of SP1010, and 19 mg of Silaace S510 were used instead of 588 mg of the composite material A1 and 112 mg of SP1010.

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

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

[Comparative Example 5]
A composition and a heat radiating member were produced 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 composite material A1 639 mg and Marcalinker S-2P 61 mg. did.

[Comparative Example 6]
A composition was prepared in the same manner as in Example 1 except that the raw material of the composition was 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 produce a heat dissipation member.

[Reference Example 1]
A composition and a heat dissipation member were produced in the same manner as in Example 1 except that the raw material of the composition was changed to 329 mg of the composite material A1 and 371 mg of the composite material B.

<Content of organic component 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 loss temperature of the heat radiating members obtained in the examples and comparative examples is the same as the measurement of the organic content, and the heating temperature is 140 to 900 ° C. when the heat radiating member is heated to 900 ° C. The weight decrease amount at 100% was taken as 100% by weight, and the temperature when the weight decreased by 5% by weight from the weight of the heat radiating member at 140 ° C. was measured. The results are shown in Table 2.

<Hygroscopic rate>
The heat radiating members obtained in Examples and Comparative Examples were dried for 2 hours under vacuum conditions 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 taken out after being held for 42 hours in a constant temperature and humidity chamber (manufactured by Espec Corp., LHL-113) at 85 ° C. and 85 RH%. g) was measured, and the moisture absorption rate of the heat radiating member was calculated by the following equation. The results are shown in Table 2.
Moisture absorption (%) = (W ₁ −W ₀ ) × 100 / W ₀

<Thermal conductivity>
The thermal conductivity was measured in advance by the specific heat of the heat radiating member (measured with a DSC type high-sensitivity differential scanning calorimeter Thermo Plus EVO2 DSC-8231, manufactured by Rigaku Co., Ltd.) and the specific gravity (manufactured by Shinko Denshi Co., Ltd. And the heat diffusivity calculated by the ai-Phase Mobile 1u thermal diffusivity measuring device manufactured by I-Phase Co., Ltd. The thermal conductivity in the thickness direction was determined. The results are shown in Table 2.

<Coefficient of thermal expansion>
Tests in the process of increasing the temperature from 50 ° C. to 250 ° C. using a TMA-SS6100 thermomechanical analyzer manufactured by SII Co., Ltd. from a heat-dissipating member obtained in the examples and comparative examples. The change in strip length was measured. The coefficient of thermal expansion (ppm / K) at 50 to 200 ° C. was determined from the change rate (ppm) of the test piece length when the length of the test piece at 50 ° C. was used as a reference. In addition, the evaluation of a dimensional change repeated the said measurement twice. Specifically, the heat dissipation member obtained above was heated to 250 ° C. (first time), then cooled to 50 ° C., and heated again to 250 ° C. (second time). Table 2 shows the calculation results of the coefficient of thermal expansion at 50 to 200 ° C. In addition, the thermal expansion behavior (temperature dependence of the rate of change in the length of the test piece) of the heat radiation member obtained in each test example at 50 to 250 ° C. is shown in FIGS.

When Example 1 and Comparative Example 1 are compared, Example 1 in which the composite material A1 is prepared using a filler and a coupling agent in advance is more heat conductive and heat resistant than Comparative Example 1 in which no composite material is formed. (5% weight loss temperature) improved. In Example 1, the fillers are covalently bonded via a coupling agent and a polymer, so that heat is easily transmitted and heat resistance is improved, whereas in Comparative Example 1, the coupling agent, This is probably because the formation of the covalent bond via the polymer is only partial. Similarly, Example 4 has improved thermal conductivity and heat resistance compared to Comparative Example 2 in which no composite material was formed. Furthermore, Example 7 has high heat conductivity and heat resistance compared with the comparative example 3 which does not use a coupling agent, and the comparative example 4 which does not form the composite material of a coupling agent and a filler.

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

Furthermore, 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 coupling agent was used. Comparative Example 6 prepared using the composite material A2 and the epoxy-based polymer resulted in inferior heat resistance, moisture absorption, and thermal conductivity as compared with the Examples. In Examples, it is considered that fillers can be covalently bonded to each other through a coupling agent and a polymer using a composite material. At this time, a polymer containing a coupling agent having oxiranyl and a ring having hydroxy is used. Is considered to be particularly effective in improving material properties.

As shown in Table 2 and FIGS. 1 to 7, the thermal expansion coefficients of Examples 1 to 7 are about 10 ppm / K from the negative thermal expansion coefficient, so that the difference in thermal expansion coefficient with other members is reduced. A heat radiating member having an appropriate coefficient of thermal expansion can be produced according to the application.

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

Claims (16)

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

   

   In the formula (1), m is an average value of 2 to 100;
   n is independently an average value of 1 or more;
   R ¹ is independently alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-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-fluorenylidene) diphenylene,
   In alkylene having 1 to 10 carbon atoms, at least one hydrogen may be replaced by —CH ₃ or hydroxy,
   Cyclohexylene, cyclohexenylene, phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, bicyclo [3.1.0] hex In —3,6-diyl and 4,4 ′-(9-fluorenylidene) diphenylene, at least one —CH ₂ — may be replaced by —O—, and at least one —CH═ is —N And at least one hydrogen may be replaced by hydroxy, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons, and having 1 to 10 carbons In the alkyl or the halogenated alkyl having 1 to 10 carbon atoms, at least one —CH ₂ — is substituted with —O—, —CO—, —COO—, or —OCO—. May be replaced;
   Ring A is a group in which at least two hydrogens are 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 by —N═, and at least one hydrogen is a halogen, an alkyl having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. In the alkyl having 1 to 3 carbon atoms or the halogenated alkyl having 1 to 3 carbon atoms, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. May be replaced by;
   

   

   In the formula (2), m is an average value of 2 to 100;
   n is independently an average value of 1 or more;
   Ring B is independently a group in 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 by —N═, and at least one hydrogen is a halogen, an alkyl having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. In the alkyl having 1 to 3 carbon atoms or the halogenated alkyl having 1 to 3 carbon atoms, at least one —CH ₂ — may be replaced with —O—, —CO—, —COO—, or —OCO—. May be replaced by;
   R ² and R ⁴ are each independently a single bond or alkylene 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 a single bond, 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-fluorenylidene) 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-fluorenylidene) diphenylene, at least one —CH ₂ — is replaced by —O—. And at least one —CH═ may be replaced by —N═, and the at least one hydrogen is hydroxy, halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons. may be replaced, at least one -CH in halogenated alkyl alkyl or C 1 -C 10 carbon number 1-10 ₂ -, -O -, - CO , It may be replaced by -COO-, or -OCO-.
4. The composition according to any one of claims 1 to 3, wherein the polymer is a polymer having hydroxy bonded to an aromatic ring in a side chain.
5. In the formula (1),
   R ¹ is independently alkylene having 1 to 10 carbon atoms, cyclohexylene, cyclohexenylene, phenylene, or naphthalene-2,6-diyl;
   Ring A is independently a group obtained by removing at least two hydrogens from benzene or naphthalene.
   The composition according to claim 3.
6. In the formula (2),
   Ring B is independently a group obtained by removing at least three hydrogens from benzene or naphthalene,
   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.
7. The composition according to any one of claims 1 to 6, wherein the polymer includes a structure derived from a monomer that does not include a ring having at least one hydroxy group selected from a (meth) acrylic compound and a vinyl compound.
8. 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.
9. The filler is at least one selected from alumina, silica, titania, zirconia, cordierite, boron nitride, boron carbide, boron nitride carbon, graphite, carbon fiber, carbon nanotube, and graphene. The composition of any one of these.
10. The composition according to any one of claims 1 to 9, wherein the coupling agent comprises oxiranyl or oxetanyl.
11. The composition according to any one of claims 1 to 10, comprising an organic compound not bonded to the filler (however, it is a compound other than a polymer containing a ring having a hydroxy group).
12. The composition according to any one of claims 1 to 11, which is used for a heat dissipation member.
13. A heat dissipating member obtained by curing the composition according to any one of claims 1 to 12.
14. A heat dissipating member according to claim 13 and an electronic device having a heat generating part,
    An electronic apparatus disposed in the electronic device such that the heat dissipation member is in contact with the heat generating portion.
15. A step a in which the first filler and the coupling agent A are combined to obtain a composite material A1,
    A method for producing a composition, comprising: composite A1 obtained in step a; and step c1 in which a polymer containing a hydroxy-containing ring is mixed.
16. A step a in which the first filler and the coupling agent A are combined to obtain a composite material A1,
    A step b1 of obtaining a composite material B1 by bonding the second filler and the coupling agent B, or
    By binding the second filler and one end of the coupling agent B and then binding the other end of the coupling agent B to the reactive compound, or binding one end of the coupling agent B and the reactive compound And then b2 to obtain the composite material B2 by bonding the other end of the coupling agent B to the second filler,
    Including 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 step c2 of mixing a polymer containing a ring having a hydroxy group. A method for producing the composition.

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