WO2019139057A1

WO2019139057A1 - Composition for heat-dissipation member, heat-dissipation member, electronic apparatus, and production method for heat-dissipation member

Info

Publication number: WO2019139057A1
Application number: PCT/JP2019/000426
Authority: WO
Inventors: 研人氏家; 武藤原
Original assignee: Jnc株式会社
Priority date: 2018-01-12
Filing date: 2019-01-10
Publication date: 2019-07-18
Also published as: JP7566467B2; JPWO2019139057A1; TW201934653A

Abstract

The present invention achieves a laminate of an organic-inorganic hybrid composite and a metal, the laminate having excellent thermal conductivity and interlayer adhesion. This composition for a heat-dissipation member contains: a first inorganic filler (11) to which one end of a first silane coupling agent (21) has been bonded; a second inorganic filler (12) to which one end of a second silane coupling agent (22) has been bonded; a third inorganic filler (13) to which one end of a third silane coupling agent (23) has been bonded; a first at least bifunctional polymerizable compound (31); and a second at least bifunctional polymerizable compound (32). Per 100 total parts by weight of the first at least bifunctional polymerizable compound (31) and the second at least bifunctional polymerizable compound (32), there are a total of 300–600 parts by weight of the first inorganic filler (11), the second inorganic filler (12), and the third inorganic filler (13).

Description

Composition for heat radiation member, heat radiation member, electronic device, method of manufacturing heat radiation member

The present invention relates to a composition for a heat dissipating member, a heat dissipating member using the same, and an electronic device. In particular, the present invention relates to a composition for a heat dissipating member which can dissipate heat by efficiently conducting and transmitting heat generated inside the electronic device, and a heat dissipating member using the composition, and an electronic device using the composition.

In recent years, in semiconductor devices for power control such as hybrid cars and electric cars, and CPUs for high-speed computers, high thermal conductivity of chip and package materials is desired so that the temperature of the internal semiconductors does not become too high. There is. That is, the ability to effectively release the heat generated from the semiconductor chip to the outside is important. In addition, due to the rise in operating temperature, thermal strain is generated due to the difference in the thermal expansion coefficient between the materials used in the chip and package, and the reduction in life due to peeling of wiring, delamination of laminated substrate, etc. becomes a problem. ing.

As a method for solving such a heat radiation problem, there is a method in which a high thermal conductivity material (heat radiation member) is brought into contact with the heat generation portion to lead the heat to the outside and radiate the heat. Patent Document 1 discloses a heat dissipation member in which an organic material and an inorganic material are compounded, and the heat dissipation member in which inorganic materials are connected by a silane coupling agent and a polymerizable liquid crystal compound (paragraph 0007). . In Reference 1, it has become possible to significantly increase the thermal conductivity between the inorganic materials by connecting the silane coupling agent and the polymerizable liquid crystal compound. However, since the reactive site of this heat dissipation member is only at the tip end of the polymerizable liquid crystal compound bonded to the silane coupling agent and at the tip end of the silane coupling agent, the silane coupling agent and the polymerizable liquid crystal compound are linked. In order to achieve this, it has been necessary to bring the distance between the fillers close to each other by applying high pressure until the sum of the chain length of the silane coupling agent and the chain length of the polymerizable liquid crystal compound. Moreover, also when using as a high thermal conductivity adhesive, it was necessary to make a filler, a filler, a filler, and a to-be-adhered body contact | adhere with high pressure, and also to make it react by heating.

Patent Document 2 discloses a die bonding paste filled with silver particles as a highly thermally conductive adhesive used in the chip package. Patent Document 3 discloses a paste of an adhesive containing solder particles. In Patent Document 4, the silver particles are sintered by heating a paste-like silver particle composition comprising non-spherical silver particles subjected to surface treatment and a volatile dispersion medium at 100 ° C. or more and 400 ° C. or less. A method of making solid silver is disclosed.
However, since the paste-like silver particle composition described in Patent Document 4 requires a coating and drying step, adhesion becomes insufficient due to the generation of spots during solvent drying and the generation of voids during sintering. There was a problem that. In addition, since these high thermal conductivity die bonding pastes use metal particles, they have a high electrical conductivity, and there is also a problem that a separate insulation process is required for the portions requiring insulation.

International Publication No. 2016/031888 JP, 2006-392834, A JP 2005-93996 A International Publication No. 2017/034833

As mentioned above, the heat dissipating member used in the chip package and various materials constituting it have been considered. However, for example, in Patent Document 1, between the inorganic filler and between the inorganic filler and the adherend, one molecule or two molecules of the silane coupling agent and a bifunctional or higher polymerizable liquid crystal compound are bonded. Therefore, as shown in FIG. 1, the bonding area is small, and the bonding strength as a whole can not be increased, and a heat dissipating member which is electrically insulating and has excellent thermal conductivity and adhesiveness with layers made of other materials is obtained. Absent. In addition, a simpler method of manufacturing the heat dissipating member has not been obtained.
From the above, the present invention provides a heat dissipation member excellent in electrical insulation and adhesiveness, which is a composite material of an organic material and an inorganic material, and further, the heat dissipation member can be more easily obtained in a small number of steps. It is an object of the present invention to provide a method for producing a heat sink component composition that can be produced.

Then, the present inventors repeated examination in order to solve the above-mentioned subject. As a result, a polymerizable compound and a polymerizable liquid crystal compound are further added to the composition for a heat dissipation member containing an organic material and an inorganic material to lengthen the bondable distance, whereby the organic material and the inorganic material are complexed. An aspect in which inorganic materials are connected with an organic material via a silane coupling agent so as to expand the adhesion area and enhance adhesion as shown in FIG. 2, that is, a silane coupling agent and an inorganic material By using a composite layer formed of a composition containing an inorganic filler and a bifunctional or higher polymerizable compound that is an organic material (hereinafter, this composite layer may be referred to as an organic-inorganic hybrid adhesion layer). The present invention has been accomplished by finding that a heat-radiating member having excellent adhesion between metal / metal, metal / semiconductor, metal / resin and the like and having extremely high thermal conductivity can be obtained.

The composition for a heat dissipation member according to the first aspect of the present invention is, as shown in FIG. 3, a first inorganic filler 11 combined with one end of a first silane coupling agent 21, a second silane coupling agent The second inorganic filler 12 bonded to one end of the second 22, the third inorganic filler 13 bonded to one end of the third silane coupling agent 23, the first bifunctional or higher polymerizable compound 31, and the second 2 A composition for a heat dissipation member containing a polymerizable compound 32 having a functionality or higher than the total amount of 100 parts by weight of the first bifunctional or higher polymerizable compound 31 and the second difunctional or higher polymerizable compound 32 The ratio of the total amount of the first inorganic filler 11, the second inorganic filler 12, and the third inorganic filler 13 is 300 to 600 parts by weight.
The “one end” may be the edge or the end of the shape of the molecule, and may or may not be the long side of the molecule.
According to this structure, a composition for heat dissipating member which can be bonded to the substrate layer such as metal or ceramic material is obtained.
When an organic-inorganic hybrid adhesive layer is formed using the composition for heat dissipation member, a laminate capable of directly propagating phonon, which is a main element of heat conduction, between the organic-inorganic hybrid adhesive layer and the substrate layer is produced. can do. The laminate can be used as a heat dissipation member and has extremely high thermal conductivity not only in the horizontal direction but also in the thickness direction. In addition, the laminate is also excellent in the adhesiveness between the organic-inorganic hybrid adhesive layer and the substrate layer. The term "phonon" as used herein refers to lattice vibration of atoms in a solid.

The composition for heat dissipation member according to the second aspect of the present invention is the composition for heat dissipation member according to the first aspect of the present invention, wherein the first inorganic filler and the second inorganic filler respectively The other end of the bound silane coupling agent is bound by at least one selected from the first bifunctional or higher polymerizable compound and the second bifunctional or higher polymerizable compound.
According to this structure, the inorganic fillers can be bonded to each other via the silane coupling agent / the polymerizable compound having two or more functions / silane coupling agent to form a laminate. Therefore, phonons, which are the main elements of heat conduction, can be directly propagated between the inorganic fillers, and between the inorganic fillers and the adherend such as the substrate layer. Furthermore, the adhesion between the organic-inorganic hybrid adhesive layer and the adherend layer is also excellent due to the increase in bonding.

The composition for heat dissipation member according to the third aspect of the present invention is the composition for heat dissipation member according to the first aspect or the second aspect of the present invention, wherein the first bifunctional or higher polymerizable compound or The second bifunctional or higher polymerizable compound includes at least two selected from the group consisting of polymerizable liquid crystal compounds represented by the following formula (1-1) and the following formula (1-2).
R ^a -Z- (A-Z) _m -R ^a (1-1)
In the above formula (1-1),
Each R ^a is independently a functional group capable of binding to the functional group at the other end of the silane coupling agent,
A each independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2, 7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, any —CH ₂ — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom It may be replaced by an alkyl of up to 10 or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—,
Z is each independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —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 any hydrogen may be replaced by halogen,
m is an integer of 1 to 6;
J-X _n -J (1-2)
In the above formula (1-2),
J is each independently a functional group capable of binding to the functional group at the other end of the above formula (1-1),
X independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2, 7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, any —CH ₂ — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom It may be replaced by an alkyl of up to 10 or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—,
n is an integer of 1 to 6.
According to this structure, it is possible to form a laminate in which an inorganic filler having a functional group such as an epoxy group on the particle surface and a substrate layer such as a metal layer are bonded via a silane coupling agent and a polymerizable liquid crystal compound. it can. Therefore, phonon, which is a main element of heat conduction in the insulating substance, can be directly propagated between the organic-inorganic hybrid adhesive layer and the adherend such as the substrate layer, and the organic-inorganic hybrid adhesive layer and It has excellent thermal conductivity between bonded bodies. Furthermore, the bond between the organic-inorganic hybrid adhesive layer and the adherend such as the substrate layer is increased, and the interlayer adhesion is also excellent.

The composition for heat dissipation member according to the fourth aspect of the present invention is the composition for heat dissipation member according to the third aspect of the present invention, wherein Z is a single bond,- CH ₂ ) _a- , -O (CH ₂ ) _a -,-(CH ₂ ) _a O-, -O (CH ₂ ) _a O-, -CH = CH-, -C≡C-, -COO-, _{-OCO -, - CH = CH-} COO -, - OCO-CH = CH -, - CH 2 CH 2 -COO -, - OCO-CH 2 CH 2 -, - CH = N -, - N = CH-, -N = N-, -OCF ₂ -or -CF ₂ O-, wherein a is an integer of 1 to 20.
According to this structure, the inorganic filler has a bond via the silane coupling agent / the polymerizable compound having two or more functional groups / silane coupling agent. Therefore, phonon, which is a main component of heat conduction, can be directly propagated between the inorganic fillers, and the organic-inorganic hybrid adhesive layer can have extremely high thermal conductivity not only in the horizontal direction but also in the thickness direction.

The composition for heat dissipation member according to the fifth aspect of the present invention is the composition for heat dissipation member according to the third aspect or the fourth aspect of the present invention, wherein in the formula (1-1), ^Ra is And each independently a polymerizable group represented by any one of the following formulas (2-1) to (2-4).

In the formulas (2-1) to (2-2), R ^b is hydrogen, halogen, —CF ₃ , alkyl having 1 to 5 carbon atoms, and q is 0 or 1.
In the above formulas (2-3) to (2-4), R ^c is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene -2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, any —CH ₂ — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom ～ 10 alkyl, or alkyl having 1 to 10 carbon atoms may be replaced, and in the alkyl, arbitrary —CH ₂ — is —O—, —CO—, —COO—, —OCO—, It may be replaced by -CH = CH- or -C≡C-. Any hydrogen may be replaced by halogen.
Each R ^d is independently hydrogen, halogen or alkyl having 1 to 5 carbon atoms.
With this configuration, the silane coupling agent can be strongly bonded to the inorganic filler.

A composition for a heat dissipation member according to a sixth aspect of the present invention is a composition for a heat dissipation member according to any one of the first to fifth aspects of the present invention, which comprises a nitride, a carbon material, and a silicified salt. The second inorganic filler is a metal oxide, and the third inorganic filler is the same as the first inorganic filler.
According to this structure, the heat dissipation member can contain a more preferable compound as an inorganic filler, and at the same time, can increase the degree of polymerization of the polymerizable compound.

The composition for heat dissipation member according to the seventh aspect of the present invention is the composition for heat dissipation member according to the sixth aspect of the present invention, wherein the first inorganic filler is boron nitride, aluminum nitride, boron carbide, At least one selected from boron nitride carbon, graphite, carbon fiber, carbon nanotube, alumina, and cordierite, and the second inorganic filler is alumina, metal nitride, zinc oxide, zirconium oxide, and titanium oxide Or at least one selected from
According to this structure, a heat dissipating member having a high thermal conductivity and a low thermal expansion coefficient can be obtained.

The composition for heat dissipation member according to the eighth aspect of the present invention is the composition for heat dissipation member according to any one of the first aspect to the seventh aspect of the present invention, wherein the first inorganic filler The modification rate of the silane coupling agent is 0.1% by weight or more.
According to this structure, the density of the composition for heat dissipation member can be increased, and the mechanical strength can be improved.

The composition for a heat dissipation member according to a ninth aspect of the present invention is the composition for a heat dissipation member according to any one of the first to eighth aspects of the present invention, wherein the first inorganic filler And a polymerizable compound not bound to the second inorganic filler.
According to this structure, in the heat dissipating member obtained by directly connecting and curing the first and second inorganic fillers, as the particle diameter of the filler is increased in order to improve the thermal conductivity of the heat dissipating member, the heat dissipating member is damaged. Thus, the porosity is increased. By filling the void with a polymerizable compound or a polymer compound that is not bonded, it is possible to improve the thermal conductivity, the water vapor blocking performance, and the like of the heat dissipation member.

The composition for a heat dissipation member according to the tenth aspect of the present invention comprises the substrate and the cured product of the composition for a heat dissipation member according to any one of the first to ninth aspects of the present invention. Is a heat dissipation member.
In such a configuration, the heat dissipation member has a bond between the inorganic fillers, and this bond does not cause molecular vibration or phase change as in ordinary resins, so that the thermal expansion has high linearity and further high thermal conductivity. You can have

An electronic device according to an eleventh aspect of the present invention includes the heat dissipation member according to the tenth aspect of the present invention and an electronic device having a heat generating portion, and the heat dissipating member is in contact with the heat generating portion. It is an electronic device disposed in an electronic device.
According to this structure, the heat dissipation member has high heat resistance and can control the thermal expansion coefficient to a high temperature, so that the thermal distortion that may occur in the electronic device can be suppressed.

According to a twelfth aspect of the present invention, there is provided a method of producing a composition for a heat dissipation member,
Bonding the first inorganic filler and one end of the first silane coupling agent;
Bonding the second inorganic filler and one end of the second silane coupling agent;
Bonding the third inorganic filler and one end of the third silane coupling agent;
A first inorganic filler bonded to one end of a first silane coupling agent, a second inorganic filler bonded to one end of a second silane coupling agent, and a third bonded to one end of a third silane coupling Adding an inorganic filler of
And a step of combining the other end of each of the silane coupling agents with a bifunctional or higher functional polymerizable compound.
According to this structure, it is possible to manufacture a heat dissipating member in which the inorganic fillers are bound to each other by the silane coupling agent and the bifunctional or higher polymerizable compound.

The composition for heat dissipation member of the present invention can be a laminate with a substrate layer such as a metal layer or a ceramic layer by curing, and has extremely high thermal conductivity and leakage of the composition for heat dissipation member. Because it is small, it has excellent adhesion between substrate layers. In addition, it has excellent properties such as chemical stability, hardness, and mechanical strength. The laminate of the present invention is suitable, for example, for a heat dissipating substrate, a heat dissipating plate (planar heat sink), a heat dissipating sheet, a heat dissipating coating, a heat dissipating adhesive, a heat dissipating insulating substrate with electrodes, a heat conductive electronic substrate, and the like. Furthermore, the method for producing a laminate of the present invention can produce a laminate of an organic / inorganic hybrid adhesive layer and a substrate layer of metal, ceramic or the like more easily with few steps.

FIG. 6 is a conceptual view showing that the inorganic filler 10 bonded to one end of the first coupling agent 21 is bonded to the substrate 1 via the first bifunctional or higher polymerizable compound 31. The inorganic filler 10 bonded to one end of the second coupling agent 22 has a first bifunctional or higher polymerizable compound 31 and a second bifunctional or higher polymerizable compound 32 and a first bifunctional or higher polymerizable compound. FIG. 6 is a conceptual view showing that it is bonded to a substrate 1 via a compound 31. The first inorganic filler 11 bonded to one end of the first coupling agent 21 and the second inorganic filler 12 bonded to one end of the second silane coupling agent 22 by curing of the composition for heat dissipation member Are bonded via the first bifunctional or higher polymerizable compound 31 and / or the second bifunctional or higher polymerizable compound 32, and the second inorganic filler 12 and the substrate 1 are bonded to the second silane cup A second bifunctional or higher polymerizable compound 31 bonded to one end of the ring agent 22, and further, a first bifunctional or higher polymerizable compound 31 and a second bifunctional or higher polymerizable compound 32; The first inorganic filler 11 bonded to one end of the first silane coupling agent 21 and the third silane cup are shown to indicate that they are bonded via the first bifunctional or higher polymerizable compound 31. One end of ring 23 The bonded third inorganic filler 13 is bonded to the other end of the first silane coupling agent 21 and the other end of the third silane coupling agent 23 and bonded to the third inorganic filler 11 A conceptual diagram showing that the substrate is bonded to the substrate 1 via the second bifunctional or higher polymerizable compound 32 bonded to the third silane coupling agent 23 and the first bifunctional or higher polymerizable compound 31 is there. It is a figure which shows the test member used for the tension test and the leak rate measurement. It is a figure which shows the cross section of the test member used for the tension test and the leak rate measurement. It is a figure which shows the upper surface of the test member used for the leak rate measurement.

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

The usage of the terms in the present specification is as follows.
“Liquid crystal compound” and “liquid crystal compound” are compounds that express a liquid crystal phase such as a nematic phase or a smectic phase.

Phrases such as “Any —CH ₂ — in alkyl may be replaced by —O— or the like” or “Any —CH ₂ CH ₂ — may be replaced by —CH = CH— or the like” The meaning is shown in the following example. For example, as a group in which arbitrary —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH = CH—, C ₃ H ₇ O—, CH ₃ —O— (CH ₂ ) ₂ -, CH ₃ -O-CH ₂ -O- and the like. Similarly, as a group in which arbitrary —CH ₂ CH ₂ — in C ₅ H ₁₁ — is replaced by —CH = CH—, H ₂ C = CH— (CH ₂ ) ₃ —, CH ₃ —CH = CH Further, as a group in which arbitrary —CH ₂ — is further replaced by —O— such as — (CH ₂ ) ₂ —, it is CH ₃ —CH = CH—CH ₂ —O— or the like. Thus, the term "arbitrary" means "at least one selected indiscriminately". In addition, in consideration of the stability of the compound, CH ₃ -O-CH ₂ -O- in which oxygen and oxygen are not adjacent to each other than CH ₃ -O-O-CH ₂ -in which oxygen and oxygen are adjacent to each other. Is preferred.

Further, the phrase “optional hydrogen may be replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons” in relation to ring A is, for example, 2 of 1,4-phenylene It means an embodiment where at least one of hydrogens at 3, 3, 5 and 6 is replaced with a substituent such as fluorine or methyl, and when the substituent is “halogenated alkyl having 1 to 10 carbon atoms” Embodiments include examples such as 2-fluoroethyl and 3-fluoro-5-chlorohexyl.

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

[Composition for heat dissipation member]
The composition for heat dissipation member includes a first inorganic filler bonded to one end of a first silane coupling agent, a second inorganic filler bonded to one end of a second silane coupling agent, and a third silane coupling A second inorganic compound having a third inorganic filler bonded to one end, a first bifunctional or higher polymerizable compound, and a second bifunctional or higher polymerizable compound, and the first bifunctional or higher polymerizable compound and the second The ratio of the total amount of the first inorganic filler, the second inorganic filler, and the third inorganic filler is 300 to 600 parts by weight with respect to 100 parts by weight of the total amount of the bifunctional or higher functional polymerizable compound.

The composition for heat dissipation members may include a combination of inorganic fillers capable of forming bonds between inorganic fillers. For example, one end of a second silane coupling agent combined with a first inorganic filler bonded to one end of a first silane coupling agent and a first and / or second bifunctional or higher polymerizable compound. A second inorganic filler bonded to a third inorganic filler bonded to a third silane coupling agent, a first bifunctional or higher polymerizable compound, and a second bifunctional or higher polymerizable compound When it contains, when the composition for thermal radiation members is hardened, inorganic fillers can be combined via a silane coupling agent and a bifunctional or higher polymerizable compound. When particles of boron nitride (h-BN) are used as the inorganic filler, when boron nitride is treated with a silane coupling agent, boron nitride has less reactive groups in the plane of the particles due to its crystal structure, so Many silane coupling agents are bonded. The boron nitride treated with a silane coupling agent can be combined with a bifunctional or higher functional polymerizable compound.
Therefore, the other end of the silane coupling agent 21 of boron nitride 11 treated with the first silane coupling agent and the other end of the polymerizable compound 22 of boron nitride 21 treated with silane coupling are bifunctional or more By bonding with a polymerizable compound, boron nitrides can be bonded to each other. On the other hand, in the case of amorphous or spherical particles in which a silane coupling agent can be bonded to the entire surface, such as alumina or aluminum nitride, bonding will increase more than boron nitride, and its use improves adhesion.
Thus, since the phonon can be directly transmitted by bonding the first and second inorganic fillers to each other via the silane coupling agent and the bifunctional or higher polymerizable compound, the cured product is extremely effective. It is possible to produce a highly heat dissipating member having high thermal conductivity and high adhesiveness.
It is important in the present invention to realize such a bond between the first inorganic filler and the second inorganic filler, and the silane coupling agent 22 and the first bifunctional or higher polymerizable compound 31 are preliminarily obtained. May be bonded using organic synthesis techniques, and then the second silane coupling agent 22 may be bonded to the second inorganic filler 12. By achieving the bond between the first inorganic filler and the third inorganic filler, the adhesion to the substrate is further enhanced, and it becomes possible to produce a heat dissipation member having high thermal conductivity.

[First bifunctional or higher polymerizable compound]
As the first bifunctional or higher polymerizable compound, it is preferable to use a bifunctional or higher polymerizable liquid crystal compound (hereinafter sometimes referred to simply as “polymerizable liquid crystal compound”).
The polymerizable liquid crystal compound is preferably a liquid crystal compound represented by the following formula (1-1), which has a liquid crystal skeleton and a polymerizable group, and has high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, etc. Have. This compound (1-1) tends to be uniform when mixed with other liquid crystalline compounds, polymerizable compounds, and the like.
R ^a -Z- (A-Z) _m -R ^a (1-1)
m is an integer of 1 to 6, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

Physical properties such as the liquid crystal phase expression region can be arbitrarily adjusted by appropriately selecting the terminal group R ^a , the ring structure A and the bonding group Z of the compound (1-1). The effects of the types of the terminal group R ^a , the ring structure A and the bonding group Z on the physical properties of the compound (1-1), and preferred examples thereof are described below.

・ Terminal group R ^a
The terminal groups R ^a may be each independently a functional group capable of binding to the functional group at the other end of the first silane coupling agent and the other end of the second silane coupling agent.
Examples thereof include, but are not limited to, a polymerizable group represented by any of the following formulas (2-1) to (2-4), cyclohexene oxide, phthalic anhydride, or succinic anhydride.

In the formulas (2-1) to (2-2), R ^b is hydrogen, halogen, —CF ₃ , or an alkyl having 1 to 5 carbon atoms, and q is 0 or 1. In the above formulas (2-3) to (2-4), R ^c is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, With tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl And in these rings, any -CH ₂ -may be replaced by -O-, any -CH = may be replaced by -N =, and any hydrogen may be halogen, carbon, It may be replaced with alkyl of 1 to 10 or alkyl of 1 to 10 carbons, and in the alkyl, arbitrary -CH ₂ -is -O-, -CO-, -COO-, -OCO -, -CH = CH-, or -C≡ - it may be replaced by. Each R ^d is independently hydrogen, halogen or alkyl having 1 to 5 carbon atoms.

Preferred R ^c is 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, Naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7 -Diyl, 9-ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7-diyl, 9,9-difluorofluorene-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. 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 and the like.

More preferable R ^c is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and the like. Particularly preferred R ^c is 1,4-cyclohexylene and 1,4-phenylene.

Furthermore, as a combination of functional groups that form a bond between the terminal group R ^a and the silane coupling agent, for example, oxiranyl and amino, oxetanyl and amino, vinyl to vinyl, methacryloxy to each other, carboxy or carboxylic anhydride residue and amine Examples include, but are not limited to, combinations of imidazole and oxiranyl, and imidazole and oxetanyl. A combination with high heat resistance is more preferable.

・ Ring structure A
When at least one ring in the ring structure A of the compound (1-1) is 1,4-phenylene, the orientational order parameter and the magnetization anisotropy are large. In the case where at least two rings are 1,4-phenylene, the temperature range of the liquid crystal phase is wide and the clearing point is high. The dielectric anisotropy is high when at least one hydrogen on the 1,4-phenylene ring is replaced by cyano, halogen, -CF ₃ or -OCF ₃ . In addition, when at least two rings are 1,4-cyclohexylene, the clearing point is high and the viscosity is small.

As preferred A, each independently, 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2,5- Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, 2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3, 6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethyl Fluorene-2,7-diyl, 9-ethyl-2,7-diyl, 9-fluoro-2,7-diyl, etc. 9,9-difluoro-2,7-diyl.

More preferable examples of A are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1 And 4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and the like. Particularly preferred A is 1,4-cyclohexylene and 1,4-phenylene.

・ Linking group Z
Bonding group Z of the compound (1-1) are each independently a single _{_{_{bond, - (CH 2) 2 -}}} , - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 - , -CH = CH -, - CF = CF- or - _(CH _{2) 4} - when it, in particular a single _{_{_{bond, - (CH 2) 2 -}}} , - CF 2 O -, - OCF 2 -, - CH = CH- or - _(CH _{2) 4} - when it, the viscosity decreases. When the bonding group Z is —CH = CH—, —CH = N—, —N = CH—, —N = N— or —CF = CF—, the temperature range of the liquid crystal phase is wide. When the bonding group Z is alkyl having about 4 to 10 carbon atoms, the melting point is lowered.

As preferred Z, each independently 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.

As further preferable Z, each independently, a single bond,-(CH ₂ ) _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -, -CH = CH-, -C≡C- and the like. Particularly preferable Z is each independently a single bond,-(CH ₂ ) _2- , -COO- or -OCO-.

The greater the number of rings in the compound (1-1), the more difficult it is to soften at high temperature, so it is preferable as the material of the composition for heat dissipation member, but if the softening temperature is higher than the polymerization temperature, molding becomes difficult. It is preferable to balance the two. In the present specification, a fused ring or the like basically comprising a 6-membered ring and a 6-membered ring is regarded as a ring, and a 3-membered ring, a 4-membered ring or a 5-membered ring alone is not regarded as a ring. In addition, a fused ring such as a naphthalene ring or a fluorene ring is regarded as one ring.

The compound (1-1) may be optically active or optically inactive. When the compound (1-1) is optically active, the compound (1-1) may have asymmetric carbon or axial asymmetry. The configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located at either ^Ra or A, and if it has an asymmetric carbon, the compatibility of the compound (1-1) is good. When the compound (1-1) has axial asymmetry, the twist induction force is large. Also, the light distribution may be any.
As described above, by appropriately selecting the types of the terminal group R ^a , the ring structure A and the bonding group Z, and the number of rings, a compound having the desired physical properties can be obtained.

・ Compound (1-1)
The compound (1-1) can also be represented as the following formula (1-a) or (1-b).
P-Y- (A-Z) _m- R ^a (1-a)
P-Y- (A-Z) _m -Y-P (1-b)

In the above formulas (1-a) and (1-b), A, Z and R ^a have the same meanings as A, Z and R ^a defined in the above formula (1-1), and P is a group of the following formula (2- 1) to a polymerizable group represented by 1 to (2-4), cyclohexene oxide, phthalic anhydride, or succinic anhydride; and Y independently represents a single bond or an alkylene having 1 to 20 carbon atoms, preferably a carbon number In the alkylene, any —CH ₂ — is substituted with —O—, —S—, —CO—, —COO—, —OCO— or —CH = CH—. Good. Particularly preferable Y is alkylene in which —CH ₂ — at one end or both ends of alkylene having 1 to 10 carbon atoms is replaced by —O—. m is an integer of 1 to 6, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

In formulas (2-1) to (2-2), R ^b is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbon atoms, and q is 0 or 1. In the above formulas (2-3) to (2-4), R ^c is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, With tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl Yes,
In these rings, any —CH ₂ — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom It may be replaced by an alkyl of up to 10 or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, optional —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—.
Each R ^d is independently hydrogen, halogen or alkyl having 1 to 5 carbon atoms.

Preferred examples of the compound (1-1) include compounds (a-1) to (a-10) and (b-1) to (b-16) and (c-1) to (c-16) shown below. ), (D-1) to (d-15), (e-1) to (e-15), (f-1) to (f-14), (g-1) to (g-20) It can be mentioned. In the formulae, * represents an asymmetric carbon.

In these formulas, R ^a , P and Y are as defined in the above formulas (1-a) and (1-b).
Z ¹ is independently a single _{_{_{_{bond, - (CH 2) 2 -}}}} , - (CF 2) 2 -, - (CH 2) 4 -, - CH 2 O -, - OCH 2 -, - (CH ₂ ) ₃ O-, -O (CH ₂ ) _3- , -COO-, -OCO-, -CH = CH-, -CF = CF-, -CH = CHCOO-, -OCOCH = CH-,-(CH _{_{2) 2 COO -, - OCO}} (CH 2) 2 -, - C≡C -, - C≡C-COO -, - OCO-C≡C -, - C≡C-CH = CH -, - CH = CH—C≡C—, —CH = N—, —N = CH—, —N = N—, —OCF ₂ —, or —CF ₂ O—. The plurality of Z ¹ may be the same or different.

Z ² are each _{_{_{_{independently, - (CH 2) 2 -}}}} , - (CF 2) 2 -, - (CH 2) 4 -, - CH 2 O -, - OCH 2 -, - (CH 2) 3 _{_{O -, - O (CH 2}} ) 3 -, - COO -, - OCO -, - CH = CH -, - CF = CF -, - CH = CHCOO -, - OCOCH = CH -, - (CH 2) 2 COO-, -OCO (CH ₂ ) _2- , -C≡C-, -C≡C-COO-, -OCO-C≡C-, -C≡C-CH = CH-, -CH = CH-C ≡C -, - CH = N - , - N = CH -, - N = N -, - OCF 2 -, or _-CF 2 is O-.

Z ³ is each independently a single bond, alkyl having 1 to 10 carbon atoms,-(CH ₂ ) _a- , -O (CH ₂ ) _a O-, -CH ₂ O-, -OCH ₂ -,- O (CH ₂ ) ₃ -,-(CH ₂ ) ₃ O-, -COO-, -OCO-, -CH = CH-, -CH = CHCOO-, -OCOCH = CH-,-(CH ₂ ) ₂ COO -, -OCO (CH ₂ ) _2- , -CF = CF-, -C≡C-, -CH = N-, -N = CH-, -N = N-, -OCF _2- , or -CF ₂ O-, and a plurality of Z ³ may be the same or different. a is an integer of 1 to 20.

X is a substituent of any hydrogen being halogen, alkyl, 1,4-phenylene which may be substituted with alkyl fluoride, or fluorene-2,7-diyl, and represents halogen, alkyl, or alkyl fluoride. .

A more preferred embodiment of the compound (1-1) is described. More preferable compound (1-1) can be represented by the following formula (1-c) or (1-d).
P ¹ -Y- (A-Z) _m -R ^a (1-c)
P ¹ -Y- (A-Z) _m -Y-P ¹ (1-d)
In the above formulae, A, Y, Z, R ^a and m are as defined above, and P ¹ represents a polymerizable group represented by any one of the following formulas (2-1) to (2-4) . In the case of the above formula (1-d), two P ¹ represent the same polymerizable groups (2-1) to (2-4), two Y represent the same group, and two Y were symmetrical. Combine to become

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

Method of Synthesizing Compounds (1-1) and (1-2) The compounds (1-1) and (1-2) can be synthesized by combining known methods in organic synthesis chemistry. For example, Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John, can be used to introduce the desired end groups, ring structures and linking groups into the starting materials. Articles such as Wily & Sons, Inc., Organic Reactions, John Wily & Sons Inc., Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. It is described in. Further, reference may be made to JP-A-2006-265527.

J-X _n- J (1-2)
In the formula (1-2), J is independently the formula (1-1) is a functional group capable of binding a functional group at the other end of, _{X n} are each independently 1, 4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2. 2) oct-1,4-diyl or bicyclo [3.1.0] hex-3,6-diyl, and in these rings, any —CH ₂ — may be replaced by —O— And any -CH = may be replaced by -N =, and any hydrogen may be replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons , In the alkyl, any -CH _2— may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—, and n is an integer of 1 to 6.

If the bifunctional or higher polymerizable compound is a polycycle, the heat resistance is high, and if the linearity is high, the elongation and fluctuation due to the heat between the inorganic fillers are small, and furthermore, the phonon conduction of heat can be efficiently transmitted. . When the linearity is high in a polycycle, the liquid crystallinity is often expressed as a result, so that it can be said that the heat conduction is improved in the case of the liquid crystallinity.
However, the polymerizable compound having two or more functional groups may be a polymerizable compound which does not exhibit liquid crystallinity other than the polymerizable liquid crystal compound represented by the above formula (1-1). For example, it exhibits liquid crystallinity due to insufficient linearity among the diglycidyl ether of polyether, the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, the diglycidyl ether of biphenol, or the compound of formula (1-1) And compounds that were not included.
The above polymerizable compounds can be synthesized by combining known methods in organic synthetic chemistry.

The polymerizable compound having two or more functional groups used in the present invention has a functional group having two or more functional groups to form a bond with a silane coupling agent, and includes a case where it is trifunctional or more and tetrafunctional or more. Furthermore, as a bifunctional or higher polymerizable compound, it is preferable to have a functional group at both ends of the long side because a linear bond can be formed.

[Inorganic filler]
Examples of the first inorganic filler, the second inorganic filler, and the third inorganic filler include nitrides, carbides, carbon materials, metal oxides, silicate minerals, etc. The third inorganic filler is a nitride, a carbide, a carbon material, a metal oxide, a silicate mineral, and the second inorganic filler is a metal oxide. The first inorganic filler, the second inorganic filler, and the third inorganic filler may be the same or different.
Specifically, as the first inorganic filler and the third inorganic filler, boron nitride, boron carbide, carbon nitride boron, graphite, carbon fibers, carbon nanotubes can be mentioned as inorganic fillers having high thermal conductivity. . Or, alumina, silica, magnesium oxide, zinc oxide, iron oxide, ferrite, mullite, cordierite, silicon nitride, and silicon carbide can be mentioned. In addition, examples of the second inorganic filler include alumina, metal nitride, zinc oxide, zirconium oxide, and titanium oxide as inorganic fillers having high thermal conductivity.

The first, second and third inorganic fillers may be mixed. The first, second, and third inorganic fillers have a functional group capable of binding to the organic functional group of the silane coupling agent on the particle surface, and the modification amount thereof is 0. 0 to the weight of the inorganic filler. It may be 1% by weight or more, preferably 0.3 to 50% by weight, and more preferably 0.5 to 25% by weight. In addition, in areas where electrical insulation is regarded as important, the use of an insulating inorganic filler results in higher reliability such as longer life, so carbon materials that are conductors and some oxides that are semiconductors are used. It is preferable not to use a thing etc.

The first and third inorganic fillers are more preferably boron nitride, aluminum nitride, silicon nitride, silicon carbide, graphite, carbon fibers, carbon nanotubes. In particular, hexagonal boron nitride (h-BN) and graphite are preferable. Boron nitride and graphite are preferable because they have a very high thermal conductivity in the planar direction and boron nitride has a low dielectric constant and high insulation. For example, it is preferable to use plate-like crystal boron nitride because the plate-like structure is easily oriented along the mold due to the flow or pressure of the raw material at the time of molding and curing.

It is desirable that the structure of the bifunctional or higher polymerizable compound have a shape and a length capable of efficiently directly bonding between these inorganic fillers. The type, shape, size, addition amount, etc. of the inorganic filler can be appropriately selected according to the purpose. When the hardened | cured material of the composition for thermal radiation members requires insulation, as long as desired insulation is maintained, it may be an inorganic filler which has conductivity. Examples of the shape of the inorganic filler include plate-like, spherical, amorphous, fibrous, rod-like and cylindrical.

The average particle size of the first, second and third inorganic fillers is preferably 0.1 to 600 μm. More preferably, it is 1 to 200 μm. A thermal conductivity is good in it being 0.1 micrometer or more, and a filling factor can be raised as it is 200 micrometers or less.
In the present specification, the average particle diameter is based on particle size distribution measurement by a laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle diameter by a wet method using analysis based on the franhofer diffraction theory and Mie's scattering theory, the diameter at which the large side and the small side become equivalent (volume based) As the median diameter.
The ratio of the inorganic filler to the silane coupling agent and the polymerizable compound depends on the amount of the silane coupling agent to be combined with the inorganic filler used. Compounds used as the first, second and third inorganic fillers (for example, boron nitride) bind as many silane coupling agents as possible to the reactive groups, and bind organic compounds equal in number or slightly more to the number of reactive groups It is preferable to The reaction amount of the silane coupling agent to the inorganic filler mainly changes depending on the size of the inorganic filler and the reactivity of the silane coupling agent used. For example, as the size of the inorganic filler increases, the area ratio of the side surfaces of the inorganic filler decreases, so the amount of modification is small. It is desirable to react as much of the silane coupling agent as possible, but it is preferable to balance as smaller particles result in lower thermal conductivity of the product.

[Silane coupling agent]
As the silane coupling agent, a silane coupling agent having a functional group to which two or more silane coupling agents can bind, or a functional group capable of binding to a functional group of a bifunctional or higher polymerizable compound, or a third one Those having a functional group capable of binding to the functional group possessed by the inorganic filler are preferred. In the case where the functional group on the other side to be bound is an oxiranyl or an acid anhydride residue, etc., it is preferable to react with the functional group, and therefore, one having an amine reactive group at the end is preferable. For example, Thyraace (registered trademark) S310, S320, S330, S360, manufactured by JNC Co., Ltd., and KBM-903, KBE-903, etc., manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned. When the terminal at the opposite side is an amine, a silane coupling agent having an oxiranyl or the like at the end is preferred. For example, in JNC Co., Ltd. product, Thyra Ace (registered trademark) S510, S530, etc. may be mentioned.
Examples of combinations of functional groups that form a bond between the silane coupling agent and the other side include combinations of oxiranyl with amino, vinyl with each other, methacryloxy with each other, carboxy or carboxylic anhydride residue with amine, imidazole with oxiranyl, etc. Although it can mention, it is not restricted to these. It may be a combination of functional groups capable of forming a bond between the silane coupling agent and the other side. A combination with high heat resistance is more preferable.
The first silane coupling agent and the second silane coupling agent may be the same or different.

[Other components]
The composition for heat dissipation member may further contain an organic compound (for example, a polymerizable compound or a polymer compound) not bound to the first inorganic filler and the second inorganic filler, that is, not contributing to the binding. , And may contain a polymerization initiator, a solvent, and the like.
In the cured product of the composition for heat dissipation member, if the porosity increases as the particle size of the filler increases in order to improve the thermal conductivity, the void is filled with a non-bonded compound It is possible to improve the thermal conductivity and the water vapor blocking performance.

[Polymerizable compound not bound]
The composition for heat dissipation members may contain a polymerizable compound (in this case, not necessarily bifunctional or more) which is not bonded to the inorganic filler as a component. As such a polymerizable compound, a compound which does not prevent the heat curing of the composition for heat dissipation member and does not evaporate or bleed out by heating is preferable. The polymerizable compounds are classified into compounds having no liquid crystallinity and compounds having liquid crystallinity. Examples of the polymerizable compound having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives and itaconic acid derivatives. As for the content, it is desirable to first prepare a composition for a heat-dissipation member which does not contain a polymerizable compound which is not bonded, measure its porosity, and add an amount of the polymerizable compound capable of filling the voids.

[Unbound polymer compound]
The composition for heat dissipation member may have a polymer compound not bound to the inorganic filler as a component. As such a high molecular compound, a compound which does not reduce film formability and mechanical strength is preferable. The polymer compound may be an inorganic filler, a silane coupling agent, and a polymer compound which does not react with the polymerizable compound. For example, when the polymerizable compound is oxiranyl and the silane coupling agent has amino, a polyolefin compound Resin, polyvinyl resin, silicone resin, wax etc. are mentioned. As for the content, it is desirable to first prepare a composition for a heat radiating member not containing a non-bonded polymer compound, measure the porosity thereof, and add a polymer compound in an amount capable of filling the voids.

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

[Polymerization initiator]
The composition for heat dissipation member may have a polymerization initiator as a component. As the polymerization initiator, for example, a photo radical polymerization initiator, a photo cationic polymerization initiator, a thermal radical polymerization initiator or the like may be used depending on the constituent elements of the composition and the polymerization method. In particular, a thermal radical polymerization initiator is preferred because the inorganic filler absorbs ultraviolet light.
Preferred initiators for thermal radical polymerization include, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide Oxides (DTBPO), t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), etc. It can be mentioned.

[solvent]
The composition for heat dissipation members may contain a solvent. When the composition which needs to be polymerized is contained in the composition, the polymerization may be carried out in a solvent or without solvent. The composition containing a solvent may be coated on a substrate by, for example, spin coating, and then the solvent may be removed and then photopolymerization may be performed. Alternatively, after photocuring, post-treatment may be performed by heating to a suitable temperature and heat curing.
Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone , Cyclohexanone, PGMEA and the like. The above solvents may be used singly or in combination of two or more.
There is no point in limiting the use ratio of the solvent at the time of polymerization, and it may be determined for each case in consideration of the polymerization efficiency, solvent cost, energy cost and the like.

[Others]
A stabilizer may be added to the composition for heat dissipation member in order to facilitate handling. The stabilizer is not particularly limited as long as the effects of the present invention are not impaired, and may be an antioxidant, a curing agent, a copper inhibitor, a metal deactivator, a tackifier, an antiaging agent, an antifoamer, Antistatic agents, weathering agents and the like can be mentioned. Antioxidants include, for example, hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
For example, when the resin forming the adhesive layer is deteriorated by contact with a metal, the addition of a copper inhibitor or a metal deactivator as mentioned in JP-A-5-48265 is preferable.
As said copper damage inhibitor (brand name), ADEKA Co., Ltd. product, Mark ZS-27, Mark CDA-16; Sanko Chemical Industries Co., Ltd. product, SANKO-EPOCLEAN; BASF company make, Irganox MD1024; etc. are preferable. .
The addition amount of the copper inhibitor is preferably 0.1 parts by weight to 100 parts by weight in total of the resin contained in the adhesive layer, from the viewpoint of preventing deterioration of the resin of the part in contact with the metal of the adhesive layer. It is up to 3 parts by weight.
Furthermore, an additive (such as an oxide) may be added to adjust the viscosity and color of the composition for heat dissipation member. For example, fine powders of titanium oxide for making white, carbon black for making black, and fine powder of silica for adjusting viscosity can be mentioned. Also, additives may be added to further increase the mechanical strength. For example, inorganic fibers or cloths such as glass fibers, carbon fibers, carbon nanotubes or the like, or as polymer additives, fibers or long molecules such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, polyimide and the like can be mentioned.

[Substrate layer]
The substrate layer forms a bond with an inorganic filler via a silane coupling agent and a bifunctional or higher functional polymerizable compound as shown in FIG. 3 to form a laminate with an organic-inorganic hybrid adhesive layer. The substrate layer can include, for example, copper, aluminum, nickel, gold, an alloy, or a ceramic. For example, when a metal layer is used as the material of the substrate layer, a bond between the organic-inorganic hybrid adhesive layer and the substrate layer is formed between the metal layer located on the outermost surface of the substrate layer and the organic-inorganic hybrid adhesive layer. Therefore, in a material having a thin film such as plating, a bond is formed between the plating material and the organic-inorganic hybrid adhesion layer via a silane coupling agent or a bifunctional or higher polymerizable compound. Thus, the metal layer may be a metal that can be a plating material. Moreover, there is no restriction | limiting in particular in the thickness of a board | substrate layer, The thickness according to a use can be used. A thicker one is preferable because of its excellent heat dissipation.

The substrate layer may be any shape or material capable of applying the composition for heat dissipation member and forming a laminate with the organic-inorganic hybrid adhesion layer formed by curing the composition for heat dissipation member. For example, as a shape, plate shape, rod shape, etc. can be mentioned.
When a metal layer is used as the material of the substrate layer, it can be used not only as a heat dissipation member but also as a metal electrode. Therefore, the metal layer may be a single metal electrode, or may be a metal electrode in a state in which one metal electrode is divided into a plurality. That is, the metal layer may be a layer composed of a plurality of metal electrodes. Thus, the laminate of the present application can also be used as an electronic substrate (printed substrate) having thermal conductivity, heat dissipation, and insulation.

[Production method]
Hereinafter, the method for producing the composition for heat dissipation member, and the method for producing a laminate from the composition and the substrate layer will be specifically described using the composition for heat dissipation member as an example.
(1) Conducting silane coupling treatment The first inorganic filler is subjected to silane coupling treatment with a first silane coupling agent to bond one end of the first silane coupling agent to the first inorganic filler. A well-known method can be used for a silane coupling process. Similarly, the second and third inorganic fillers can be subjected to the silane coupling treatment with the second and third silane coupling agents.
As an example, first, the inorganic filler and the silane coupling agent are added to the solvent. After stirring using a stirrer etc., it dries. After solvent drying, heat treatment is performed under vacuum conditions using a vacuum dryer or the like. A solvent is added to the inorganic filler, and the mixture is crushed by ultrasonication. The solution is separated and purified using a centrifuge. After discarding the supernatant, the solvent is added and the same operation is repeated several times. The dried inorganic coupling-treated filler is dried using an oven.
(2) Modification with Bifunctional or Higher Polymerizable Compound The second inorganic filler was subjected to a silane coupling treatment with a second silane coupling agent (or was subjected to a silane coupling treatment with a first silane coupling agent) The first inorganic filler may be used as a second inorganic filler), and the other terminal of the second silane coupling agent is further bonded to a first bifunctional or higher polymerizable compound.
As an example, after mixing the inorganic filler by which the silane coupling process was carried out, and the polymeric compound more than a 2nd functional using an agate mortar etc., it knead | mixes using 2 rolls etc. It is then separated and purified by sonication and centrifugation.
(3) Mixing The first inorganic filler bonded to one end of the first silane coupling agent, the second inorganic filler bonded to one end of the second silane coupling agent, and the third silane coupling agent The third inorganic filler bonded to one end of the mixture is weighed, for example, so that the weight of the inorganic filler alone is 1: 1: 1, and mixed in an agate mortar or the like. Then, it mixes using 2 rolls etc. and obtains the composition for thermal radiation members.
A first inorganic filler bonded to one end of a first silane coupling agent, a second inorganic filler bonded to one end of a second silane coupling agent, and one end of a third silane coupling agent When the bonding ratio with the third inorganic filler is such that the bonding group forming the bond between the first inorganic filler and the second inorganic filler is respectively amine: epoxy, the weight of only the inorganic filler is, for example, 1 by weight ratio It is preferably 0.1 to 1:30, more preferably 1: 3 to 1:20. More preferably, it is 1: 4 to 1:10. The mixing ratio is determined by the number of terminal bonding groups that form a bond between the first inorganic filler and the second inorganic filler, and for example, a primary amine can react with two oxiranyl, so The amount may be relatively small, and the oxiranyl side may be open, and it is preferable to use a larger amount calculated from the epoxy equivalent.

The temperature during compression molding is in the range of room temperature to 350 ° C., preferably room temperature to 300 ° C., more preferably 50 ° C. to 250 ° C., and the time is 5 seconds to 10 hours, preferably 1 minute to 5 hours, Preferably, it is in the range of 5 minutes to 1 hour. After curing, it is preferable to gradually cool in order to suppress stress distortion and the like. Further, reheating treatment may be performed to reduce distortion and the like. As described above, the formation of the organic-inorganic hybrid adhesive layer and the bonding of the organic-inorganic hybrid adhesive layer and the substrate layer (metal layer) can be performed by thermocompression bonding at a relatively low temperature.
The thickness of the organic-inorganic hybrid adhesive layer is preferably thin in order to improve the thermal conductivity in the vertical direction. Preferably, it is 30 μm to 2000 μm, more preferably 30 μm to 1000 μm. More preferably, it is 30 μm to 500 μm. The film thickness of the organic-inorganic hybrid adhesive layer and the substrate layer (metal layer) may be appropriately changed depending on the application.

As mentioned above, the heat radiating member of this invention is a laminated body which has the organic-inorganic hybrid adhesion layer and substrate layer (metal layer) which are the hardened | cured material which hardened the composition for heat radiating members. The cured product of the composition for heat dissipation member has high thermal conductivity and has a negative to positive thermal expansion coefficient depending on the type of organic material and inorganic material used, the compounding ratio, curing conditions, etc., and is chemically stable. Superior in hardness, hardness and mechanical strength. The mechanical strength includes Young's modulus, tensile strength, tear strength, flexural strength, flexural modulus, impact strength and the like.
The heat dissipation member of the present invention is useful for a heat dissipation plate, a heat dissipation sheet, a heat dissipation film, a heat dissipation adhesive, a heat dissipation molded product, and the like. Furthermore, it can also be used as an electronic substrate (printed substrate) having thermal conductivity, heat dissipation, and insulation.

[Electronics]
The electronic device of the present invention includes the heat dissipation member of the present invention and an electronic device having a heat generating portion. The heat dissipation member is disposed in the electronic device so as to contact the heat generating portion. The mode of the heat dissipating member may be any of a heat dissipating electronic substrate, a heat dissipating plate, a heat dissipating sheet, a heat dissipating film, a heat dissipating adhesive, a heat dissipating molded product, and the like.
For example, a semiconductor element can be mentioned as an electronic device. The heat radiating member of the present invention has high heat resistance and high insulation in addition to high thermal conductivity. Therefore, the semiconductor device is particularly effective for power semiconductors such as silicon carbide, silicon nitride, gallium nitride, gallium oxide and diamond, which require a more efficient heat dissipation mechanism because of high power. Electronic devices equipped with these power semiconductors include main conversion elements of large power inverters, uninterruptible power supplies, variable voltage variable frequency controllers for AC motors, controllers for railway vehicles, electric vehicles such as hybrid cars and electric cars, etc. Equipment, IH cooker, etc. can be mentioned.

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 component materials used in the examples of the present invention are as follows.

<Inorganic filler>
-Boron nitride: h-BN particles, manufactured by Momentive Performance Materials Japan (O), (trade name) PolarTherm PTX-25
・ Alumina ・ Nippon Light Metal Co., Ltd. made, (trade name) Nikkkei FS-210B
・ Nippon Light Metal Co., Ltd. (trade name) Nichigane FS-243
-Nippon Light Metal Co., Ltd. product (trade name) Nichigane FS-711C
-Nippon Light Metal Co., Ltd. (trade name) Nikkei Random V 325 F
-Nippon Light Metal Co., Ltd. (trade name) Polyhedral alumina CT50
-Denka Co., Ltd. product (trade name) DAW-20

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

3-Glycidoxypropyltrimethoxysilane, manufactured by JNC Co., Ltd., (trade name) Thyraace (registered trademark) S510

<Bifunctional or Higher Polymerizable Compound>
Polymerizable oxiranyl compounds, manufactured by JNC Co., Ltd., the following formula (1-11)

(1-11)

・ Polymerizable oxiranyl compound, manufactured by Mitsubishi Chemical Corporation, (trade name) jER 807

・ Polymerizable amine compound, 4,4'-diamino-1,2-diphenylmethane, manufactured by Wako Pure Chemical Industries, Ltd.

・ Polymerizable amine compound, 4,4'-ethylenedianiline, manufactured by Tokyo Chemical Industry Co., Ltd.

<Substrate layer>
The copper plate was used as a DCB substrate, and the aluminum plate was used as a DBA substrate.
・ Copper foil, manufactured by Furukawa Electric Co., Ltd. (trade name) FS-WS
・ Copper plate: Size 4 × 4 cm, thickness 400 μm
-Aluminum plate: Size 4 x 4 cm, thickness 400 μm

Example 1
-Modified filler preparation process 10 g of boron nitride particles (Polaritive Performance Materials Japan (combined) made by PolarTherm PTX-25) as the first inorganic filler, and as the first silane coupling agent, manufactured by JNC Co., Ltd. 1 g of Silaace (registered trademark) S320 was added to 100 mL of toluene, and the mixture was stirred at 500 rpm for 1 hour using a stirrer, and the resulting mixture was dried at 40 ° C. for 4 hours. Furthermore, it heat-processed under vacuum conditions for 5 hours using the vacuum dryer set to 120 degreeC after solvent drying. The resulting particles are the first inorganic filler bonded to one end of the first silane coupling agent, and this is referred to as the modified filler X.
In the same manner, using alumina particles (Nippon Light Metal Co., Ltd. Nippon Light Metal LS-210B) in place of the above PTX-25, the obtained particles are bonded to one end of the second silane coupling agent. The inorganic filler of No. 2 is referred to as modified filler Y.
In place of the silane coupling agent S320 of the modified filler X, 2.5 g of a silane coupling agent (JNC Co., Ltd. Sila Ace (registered trademark) S510) is added to 125 g of pure water and stirred at 500 rpm for 15 hours using a stirrer did. Next, 12.5 g of boron nitride particles (Polaritive Performance Japan Co., Ltd. PolarTherm PTX-25) is added to the solution, and stirred at 500 rpm for 1 hour using a stirrer, and the obtained mixture is heated at 60 ° C. 4 Dried for hours. After drying, heat treatment was performed for 5 hours under vacuum conditions using a vacuum oven set at 80 ° C. The resulting particles are the third inorganic filler bonded to one end of the third silane coupling agent, and this is referred to as the modified filler Z.

-Composition preparation process for heat dissipation member 0.9 g of modified filler particle X, 2 g of modified filler particle Y, 0.1 g of modified filler particle Z, compound manufactured by JNC Co., Ltd. as a first bifunctional or higher polymerizable compound 0.6 g of (1-11) and 0.3 g of 4,4′-diamino-1,2-diphenylmethane as a second bifunctional or higher polymerizable compound were weighed out and mixed at room temperature. The obtained mixture is a composition for heat dissipation members.

-Preparation of heat dissipation member (1) Weighed 0.2 g of the composition for heat dissipation member and placed it on the lower part (1.65 cm x 4 cm) of an aluminum plate (4 cm x 4 cm x 400 μm) using this as a base material Place the same aluminum plate so as to overlap only on the part, sandwich it, press it to 20 MPa using a compression molding machine (mini test press-10 small heat press manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 150 ° C. Alignment treatment and curing were performed by continuing heating for 15 minutes. That is, when the composition for heat dissipation member spreads between the aluminum plates, the boron nitride particles are plate-like particles, so the boron nitride particles and the aluminum plate are oriented so as to be parallel to each other. Further, the amount of the composition for heat dissipation member was adjusted so that the thickness of the laminate of the layer of aluminum plate / composition for heat dissipation member / aluminum plate was about 1 mm. The obtained laminate was used as a heat dissipation member (1).

-Preparation of heat dissipation member (2) Weigh out 0.1 g of the composition for heat dissipation member, place it on a copper foil (5 cm x 5 cm x 35 μm) using this as a base material, place similar copper foil and sandwich so as to overlap Using a compression molding machine (mini test press-10 small heat press manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 150 ° C., pressurize to 20 MPa and continue heating for 15 minutes to perform alignment treatment and curing The That is, when the composition for heat dissipation member spreads between the copper foils, the boron nitride particles are plate-like particles, and therefore, the boron nitride particles and the copper foil are oriented in parallel. Further, the amount of the composition for heat dissipation member was adjusted such that the thickness of the laminate of the layer of the composition for copper foil / the composition for heat dissipation member / copper foil was about 300 μm. The obtained laminate was used as a heat dissipation member (2).

<Evaluation of leak degree of adhesive member (leak rate)>
Generally, when bonding is performed under pressure using a mixture of a resin component such as a polymerizable compound and an inorganic filler, there is a problem that the inorganic filler component remains between adherends and extra resin component leaks to the periphery. Occur. However, by taking the structure as shown in FIG. 1 of the present invention, it is possible to solve the problem that the resin component and the inorganic filler are separated. Conversely, the fact that the amount of the leaked resin component is small is considered to be the structure shown in FIG.
The degree of leakage of the adhesive member was confirmed as follows.
In the heat radiating member (1), as shown in FIG. 6, a value obtained by multiplying the area obtained by the leakage by the area to be bonded and the value 100 is calculated as the leakage rate.
<Peel strength measurement>
The tensile test was conducted as follows, and the peel strength was confirmed.
In the heat dissipating member (1), as shown in FIGS. 4 and 5, the non-adhered portions of the two aluminum plates are sandwiched vertically, and a tensile test measurement machine (AGS-X tensile tester manufactured by Shimadzu Corporation) Was pulled at a speed of 5 mm / min, and the tension at break was measured. When it did not break, it was made more than the detection limit (1000 N).
<Measurement of thermal diffusivity>
Using a heat dissipation member (2), the thermal diffusivity was measured with ai-Phase Mobile 1u thermal diffusivity device manufactured by I-phase.

Example 2
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylenedianiline was used as a second bifunctional or higher polymerizable compound. Production and evaluation were performed in the same manner as in Example 1 except for the above.

[Example 3]
Nichigane LS-243 was used as a second inorganic filler instead of Nichigane LS-210B. Production and evaluation were performed in the same manner as in Example 1 except for the above.

Example 4
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylenedianiline was used as a second bifunctional or higher polymerizable compound. Production and evaluation were performed in the same manner as in Example 3 except for the above.

[Example 5]
Nichigane LS-711C was used as a second inorganic filler instead of Nichigane LS-210B. Production and evaluation were performed in the same manner as in Example 1 except for the above.

[Example 6]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylenedianiline was used as a second bifunctional or higher polymerizable compound. Except for this, preparation and evaluation were performed in the same manner as in Example 5.

[Example 7]
Nikkei random V325F was used as a second inorganic filler in place of the light weight LS-210B. Production and evaluation were performed in the same manner as in Example 1 except for the above.

[Example 8]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylenedianiline was used as a second bifunctional or higher polymerizable compound. Production and evaluation were performed in the same manner as in Example 7 except for the above.

[Example 9]
Polyhedral alumina CT50 was used in place of the light-light LS-210B. Production and evaluation were performed in the same manner as in Example 1 except for the above.

[Example 10]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylenedianiline was used as a second bifunctional or higher polymerizable compound. Production and evaluation were performed in the same manner as in Example 9 except for the above.

[Example 11]
DAW-20 was used in place of light duty LS-210B. Production and evaluation were performed in the same manner as in Example 1 except for the above.

[Example 12]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylenedianiline was used as a second bifunctional or higher polymerizable compound. Except this, preparation and evaluation were performed similarly to Example 11.

Comparative Example 1
Epicoat jER 807 was used instead of JNC Co., Ltd. compound (1-11). Except this, preparation and evaluation were performed similarly to Example 11.

The evaluation results of Examples and Comparative Examples are shown in Table 1.
Moreover, the composition of the composition for thermal radiation members of an Example and a comparative example was shown in Table 2.

As shown in Table 1 above, when the compound (1-11) manufactured by JNC Co., Ltd. is used as the first bifunctional or higher polymerizable compound, the adhesion with the metal layer which is the substrate layer is high, and it is for heat dissipation members There was also little leakage of the composition, and the thermal diffusivity in the vertical direction became a high value. The adhesion was particularly good when 4,4'-ethylenedianiline having an amino group was used.
Compared with this, the one using the epicoat jER 807, which is a polymerizable oxiranyl compound, as the first bifunctional or higher polymerizable compound, the leakage of the composition for heat radiation member is extremely severe, and this affects the metal that is the substrate layer. Adhesion to the layer was poor, and at the same time, the thermal diffusivity was lowered.

REFERENCE SIGNS LIST 1 substrate 10 inorganic filler 11 first inorganic filler 12 second inorganic filler 13 third inorganic filler 21 first silane coupling agent 22 second silane coupling agent 23 third silane coupling agent 31 first The bifunctional or higher functional polymerizable compound 32 The metal plate 42 on the second bifunctional or higher polymerizable compound 41 The composition for the heat radiating member 43 The metal plate 51 below The bonding surface 52 For the heat radiating member leaking from the bonding surface Composition 61 Area to be bonded 62 Area leaked

Claims

A first inorganic filler bonded to one end of a first silane coupling agent, a second inorganic filler bonded to one end of a second silane coupling agent, a third bonded to one end of a third silane coupling It is a composition for heat dissipation members containing an inorganic filler, a first bifunctional or higher polymerizable compound, and a second bifunctional or higher polymerizable compound,
The first inorganic filler, the second inorganic filler, and the third inorganic based on 100 parts by weight of the first bifunctional or higher polymerizable compound and the second bifunctional or higher polymerizable compound. A composition for a heat dissipating member, wherein the ratio of the total amount of fillers is 300 to 600 parts by weight.
The other end of the silane coupling agent in which the first inorganic filler and the second inorganic filler are bonded to each other, the first bifunctional or higher polymerizable compound and the second bifunctional or higher polymerization The composition for heat dissipation members according to claim 1, wherein the composition is bound by at least one compound selected from the group consisting of
A group in which the first bifunctional or more polymerizable compound or the second bifunctional or more polymerizable compound is a polymerizable liquid crystal compound represented by the following formula (1-1) and the following formula (1-2) Containing at least two selected from
The composition for heat dissipation members according to claim 1 or 2.
R a -Z- (A-Z) m -R a (1-1)
[In the above formula (1-1),
Each R a is independently a functional group capable of binding to the functional group at the other end of the silane coupling agent,
A each independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2, 7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, any —CH 2 — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom It may be replaced by an alkyl of up to 10 or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH 2 — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—,
Z is each independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —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 arbitrary hydrogen may be replaced by halogen,
m is an integer of 1 to 6; ]
J-X n -J (1-2)
[In said Formula (1-2),
J is each independently a functional group capable of binding to the functional group at the other end of the above formula (1-1),
X independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2, 7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, any —CH 2 — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom It may be replaced by an alkyl of up to 10 or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH 2 — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—,
n is an integer of 1 to 6. ]
In the formula (1-1), Z is a single bond, - (CH 2) a - , - O (CH 2) a -, - (CH 2) a O -, - O (CH 2) a O- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -CH 2 CH 2 -COO-, -OCO-CH 2 CH 2- , -CH = N-, -N = CH-, -N = N-, -OCF 2- , or -CF 2 O-, wherein a is an integer of 1 to 20,
The composition for heat dissipation members according to claim 3.
5. The method according to claim 3, wherein in the formula (1-1), each R a is a polymerizable group represented by any one of the following formulas (2-1) to (2-4). The composition for thermal radiation members as described.

In the above formulas (2-1) to (2-2), R b is hydrogen, halogen, —CF 3 , an alkyl having 1 to 5 carbon atoms, and q is 0 or 1.
In the above formulas (2-3) to (2-4), R c is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene -2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl,
In these rings, any —CH 2 — may be replaced by —O—, and any —CH = may be replaced by —N =, and any hydrogen may be halogen, one carbon atom It may be replaced by an alkyl of up to 10 or an alkyl halide having 1 to 10 carbon atoms,
In the alkyl, optional —CH 2 — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH = CH—, or —C≡C—.
Each R d is independently hydrogen, halogen or alkyl having 1 to 5 carbon atoms. ]
The first inorganic filler is a nitride, a carbon material, a silicate, or a metal oxide, the second inorganic filler is a metal oxide, and the third inorganic filler is the first inorganic filler. Same as the inorganic filler of
The composition for a heat dissipation member according to any one of claims 1 to 5.
The first inorganic filler is at least one selected from boron nitride, aluminum nitride, boron carbide, boron carbon nitride, graphite, carbon fiber, carbon nanotube, alumina, and cordierite, and the second inorganic filler Is at least one selected from alumina, metal nitrides, zinc oxide, zirconium oxide, and titanium oxide,
The composition for heat dissipation members according to claim 6.
The modification rate of the silane coupling agent of the first inorganic filler is 0.1% by weight or more.
A composition for a heat dissipation member according to any one of claims 1 to 7.
It further comprises a polymerizable compound not bound to the first inorganic filler and the second inorganic filler,
A composition for a heat dissipation member according to any one of claims 1 to 8.
A heat dissipating member comprising the cured product of the composition for heat dissipating member according to any one of claims 1 to 9 and a substrate layer.
A heat dissipation member according to claim 10,
And an electronic device having a heat generating portion,
The heat dissipation member is disposed in the electronic device such that the heat dissipation member contacts the heat generating portion;
Electronics.
Bonding the first inorganic filler and one end of the first silane coupling agent;
Bonding the second inorganic filler and one end of the second silane coupling agent;
Bonding the third inorganic filler and one end of the third silane coupling agent;
A first inorganic filler bonded to one end of a first silane coupling agent, a second inorganic filler bonded to one end of a second silane coupling agent, and a third bonded to one end of a third silane coupling Adding an inorganic filler of
Combining the other end of each of the silane coupling agents with a bifunctional or higher functional polymerizable compound,
The manufacturing method of the composition for thermal radiation members.