TW201934653A - Composition for heat-dissipation member, heat-dissipation member, electronic apparatus, and production method for heat-dissipation member - Google Patents

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, and method for manufacturing heat radiation member

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

In recent years, semiconductor devices for power control, such as hybrid vehicles and electric automobiles, or central processing units (CPUs) for high speed computers have been developed in order to The internal semiconductor temperature is not excessively high, and high thermal conductivity of wafers and packaging materials is desired. That is, the ability to efficiently release heat generated from a semiconductor wafer to the outside becomes important. In addition, due to the increase in operating temperature, thermal strain occurs due to the difference in the thermal expansion coefficient between the materials used in the wafer and the package, and reduction in life due to peeling of wiring and layer peeling of the laminated substrate becomes a problem.

As a method for solving such a heat radiation problem, a method in which a highly thermally conductive material (radiation member) is brought into contact with a heat-generating portion, and heat is dissipated to the outside to dissipate heat is mentioned. Patent Document 1 discloses a heat-dissipating member that is a composite of an organic material and an inorganic material, and connects the inorganic material with a silane coupling agent and a polymerizable liquid crystal compound (paragraph 0007). In Reference 1, by using a silane coupling agent to connect to a polymerizable liquid crystal compound, the thermal conductivity between inorganic materials can be significantly improved. However, the reactive portion of the heat dissipation member is only the front end portion of the polymerizable liquid crystal compound bonded to the silane coupling agent and the front end portion of the silane coupling agent. Therefore, in order to connect the polymerizable liquid crystal compound by the silane coupling agent, it is necessary to apply The pressure is so high that the distance between the fillers is shortened to a length that becomes the sum of the chain length of the silane coupling agent and the chain length of the polymerizable liquid crystal compound. In addition, when it is used as a highly thermally conductive adhesive, it is also necessary to make the filler and the filler and the filler and the adherend adhere to each other by high pressure, and then react by heating.

Patent Document 2 discloses a die bonding paste filled with silver particles as a highly thermally conductive adhesive used in the wafer and package. In addition, Patent Document 3 discloses a paste of an adhesive containing solder particles. Further, Patent Document 4 discloses a method in which a paste-like silver particle composition containing non-spherical silver particles and a volatile dispersion medium subjected to surface treatment is heated at a temperature of 100 ° C or higher and 400 ° C or lower, and the silver particles are sintered. Method for forming solid silver.
However, since the paste-like silver particle composition described in Patent Document 4 requires a coating or drying step, there is a problem in that the adhesiveness is insufficient due to unevenness during solvent drying or voids during sintering. In addition, these highly thermally conductive pastes use metal particles, so they have high electrical conductivity, and they also have the problem of requiring additional insulation processing at the parts that need insulation.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2016/031888
[Patent Document 2] Japanese Patent Laid-Open No. 2006-392834
[Patent Document 3] Japanese Patent Laid-Open No. 2005-93996
[Patent Document 4] International Publication No. 2017/034833

[Problems to be Solved by the Invention]
As described above, the heat dissipation members used in wafers and packages and various materials constituting them have been studied. However, for example, in Patent Document 1, since one or two molecules of a silane coupling agent and two or more functional polymerizable liquid crystal compounds are used to bond between inorganic fillers and between an inorganic filler and an adherend, as shown in FIG. 1 In general, the bonding area is small, and the overall bonding strength cannot be improved, so that a heat-radiating member having excellent electrical insulation and thermal conductivity and excellent adhesion to a layer containing other raw materials cannot be obtained. In addition, it is not possible to obtain an easier method for manufacturing a heat dissipation member.
In view of the foregoing, an object of the present invention is to provide a heat-dissipating member having excellent electrical insulation and adhesiveness, including a composite material of an organic material and an inorganic material, and further, to provide a method that can be more easily manufactured with fewer steps. A method for producing a heat radiation member composition.
[Means for solving problems]

Therefore, the present inventors have repeatedly studied to solve the problems. As a result, it was found that by adding a polymerizable compound and a polymerizable liquid crystal compound to a composition for a heat-dissipating member containing an organic material and an inorganic material, the bondable distance is extended to make the composite of the organic material and the inorganic material useful. Inorganic materials are connected to each other via a silane coupling agent and organic materials, so that the bonding area is enlarged as shown in FIG. 2 to increase the bonding force, that is, an inorganic filler containing a silane coupling agent, as an inorganic material, and as A composite layer formed of a composition of a bifunctional or more polymerizable compound of an organic material (hereinafter, this composite layer may be referred to as an organic-inorganic mixed adhesive layer), thereby obtaining a metal / metal space, a metal / semiconductor space, and a metal. A heat dissipating member having excellent adhesion between resins and the like and extremely high thermal conductivity has completed the present invention.

As shown in FIG. 3, the composition for a heat dissipation member according to a first aspect of the present invention includes a first inorganic filler 11 bonded to one end of a first silane coupling agent 21 and a end bonded to one end of a second silane coupling agent 22. The second inorganic filler 12, the third inorganic filler 13 bonded to one end of the third silane coupling agent 23, the first bi-functional polymerizable compound 31, and the second bi-functional polymerizable compound 32, wherein: The first inorganic filler 11 and the second inorganic filler 12 with respect to 100 parts by weight of the total amount of the first and second functional polymerizable compounds 31 and the second and second functional polymerizable compounds 32. And the ratio of the total amount of the third inorganic filler 13 is 300 parts by weight to 600 parts by weight.
The "one end" may be an edge or an end of a molecular shape, and may be both ends of the long side of the molecule or not both ends of the long side of the molecule.
With such a configuration, a composition for a heat dissipating member that can be adhered to a substrate layer such as a metal or a ceramic material can be obtained.
By using the composition for a heat dissipating member to form an organic-inorganic hybrid adhesive layer, a laminated body capable of directly propagating a phonon as a main element of heat conduction between the organic-inorganic hybrid adhesive layer and the substrate layer can be produced. The laminated body 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 laminated body has excellent adhesion between the organic-inorganic mixed adhesive layer and the substrate layer. The term “phonon” used herein refers to the lattice vibration of atoms in a solid.

The second aspect of the present invention is a composition for a heat dissipating member, as in the first composition of the present invention for a heat dissipating member, wherein the first inorganic filler and the second inorganic filler utilize silanes bonded to each other. The other end of the coupling agent and at least one selected from the first di- or more-functional polymerizable compound and the second di- or more-functional polymerizable compound are bonded.
With such a configuration, the inorganic filler can be bonded to each other via the silane coupling agent / 2 functional polymerizable compound / silane coupling agent to form a laminate. Therefore, it is possible to directly propagate phonons, which are the main elements of heat conduction, between the inorganic fillers, and between the inorganic filler and the substrate layer. Furthermore, the organic-inorganic mixed adhesive layer and the adhered layer are also excellent in adhesiveness due to an increase in bonding.

A third aspect of the present invention is a composition for a heat dissipating member as described in the first aspect or the second aspect of the present invention, wherein the first di- or more functional polymerizable compound or the first The di- or more-functional polymerizable compound includes at least two kinds selected from the group consisting of a polymerizable liquid crystal compound represented by the following formula (1-1) and the following formula (1-2).

R ^a -Z- (AZ) _m -R ^a (1-1)

In the formula (1-1),
R ^{a is} each independently a functional group capable of being bonded to a functional group at the other end of the silane coupling agent,
A is independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl , Fluorene-2,7-diyl, bicyclic [2.2.2] oct-1,4-diyl, or bicyclic [3.1.0] hexan-3,6-diyl,
In these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, and any hydrogen may be halogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Haloalkyl substitution,
In the alkyl group, any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-,
Z is independently a single bond or an alkylene group having 1 to 20 carbon atoms,
In the alkylene group, any -CH ₂ -may be -O-, -S-, -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, -CH = N -, -N = CH-, -N = N-, -N (O) = N-, or -C≡C-, any hydrogen can be replaced by halogen,
m is an integer from 1 to 6.

JX _n -J (1-2)

In the formula (1-2),
J are each independently a functional group capable of bonding to a functional group at the other end of the formula (1-1),
X is independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl , Fluorene-2,7-diyl, bicyclic [2.2.2] oct-1,4-diyl, or bicyclic [3.1.0] hexan-3,6-diyl,
In these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, and any hydrogen may be halogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Haloalkyl substitution,
In the alkyl group, any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-,
n is an integer from 1 to 6.
With such a configuration, a laminate can be formed in which an inorganic filler having a functional group such as an epoxy group on the surface of a particle is bonded to a substrate layer such as a metal layer via a silane coupling agent and a polymerizable liquid crystal compound. Therefore, a phonon, which is a main element of heat conduction in an insulating substance, can be directly transmitted between an adherend such as an organic-inorganic hybrid adhesive layer and a substrate layer, and has excellent thermal conductivity between the organic-inorganic hybrid adhesive layer and the adherend. Furthermore, the bond between an organic-inorganic mixed adhesive layer and an adherend such as a substrate layer increases, and the layer indirect adhesion is also excellent.

The fourth aspect of the present invention is a composition for a heat dissipating member as described in the third aspect of the present invention, wherein 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-, and a is an integer of 1-20.
When comprised in this way, the inorganic filler has a bond via the silane coupling agent / 2 functional polymerizable compound / silane coupling agent. Therefore, phonons, which are the main elements of thermal conduction, can be directly propagated between the inorganic fillers, and the organic-inorganic mixed adhesive layer can have extremely high thermal conductivity not only in the horizontal direction but also in the thickness direction.

The fifth aspect of the present invention is a composition for a heat dissipating member as described in the third aspect or the fourth aspect of the present invention, wherein R ^a in the formula (1-1) is It is independently a polymerizable group represented by any one of the following formulae (2-1) to (2-4).



In the formulae (2-1) to (2-2), R ^b is hydrogen, halogen, -CF ₃ , or an alkyl group having 1 to 5 carbon atoms, and q is 0 or 1.
In the formulae (2-3) to (2-4), R ^c is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2, 6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2.2] octane-1,4-diyl, or bicyclic [3.1.0] hexan-3 , 6-diyl,
In these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, and any hydrogen may be halogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Halogenated alkyl substitution, in which any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-. Arbitrary hydrogen may be substituted by halogen.
R ^{d is} each independently hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms.
With this structure, the silane coupling agent can be firmly bonded to the inorganic filler.

The sixth aspect of the present invention is a composition for a heat dissipating member as described in any one of the first aspect to the fifth aspect of the present invention, wherein the composition is a nitride, a carbon material, or silicon. A salt or a metal oxide, the second inorganic filler is a metal oxide, and the third inorganic filler is the same as the first inorganic filler.
With such a configuration, the heat dissipating member can contain a compound that is more preferable as the inorganic filler, and at the same time, the degree of polymerization of the polymerizable compound can be improved.

A composition for a heat dissipation member according to a seventh aspect of the present invention is the composition for a heat dissipation member according to the sixth aspect of the present invention, wherein the first inorganic filler is selected from the group consisting of boron nitride, aluminum nitride, and carbonization. Boron, boron carbon nitrogen, graphite, carbon fiber, carbon nanotube, alumina, and cordierite, the second inorganic filler is selected from alumina, metal nitride, zinc oxide, and oxide At least one of zirconium and titanium oxide.
With such a configuration, a heat radiation member having a high thermal conductivity and a small thermal expansion coefficient can be obtained.

An eighth aspect of the present invention is a composition for a heat dissipating member as described in any one of the first aspect to the seventh aspect of the present invention, wherein the silane of the first inorganic filler is The modification ratio of the coupling agent is 0.1% by weight or more.
With such a configuration, the density of the composition for a heat dissipation member can be increased, and the mechanical strength can be improved.

The ninth aspect of the present invention is a composition for a heat dissipating member, which is any one of the first aspect to the eighth aspect of the present invention, and further includes the first inorganic filler. And a polymerizable compound to which the second inorganic filler is not bonded.
With such a structure, it is as follows: In a heat radiating member obtained by directly connecting and hardening the first inorganic filler and the second inorganic filler, the particle diameter of the filler is increased as the thermal conductivity of the heat radiating member is increased, The porosity will increase correspondingly. By filling the gap with an unbonded polymerizable compound or a polymer compound, the thermal conductivity of the heat dissipation member, the water vapor blocking performance, and the like can be improved.

A tenth aspect of the present invention includes a hardened member of the heat dissipation member composition of any one of the first to ninth aspects of the present invention, and a substrate layer.
With such a configuration, the heat dissipating member has a bond between the inorganic fillers, and the bond does not cause molecular vibration or phase change like ordinary resins. Therefore, the linearity of thermal expansion is high, and further, it can have high thermal conductivity.

An electronic device according to an eleventh aspect of the present invention includes the heat dissipating 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 disposed in contact with the heat generating portion In the electronic device.
With such a configuration, the heat dissipation member has good heat resistance, and the thermal expansion coefficient can be controlled even at high temperatures. Therefore, it is possible to suppress thermal strain that may occur in an electronic device.

A method for manufacturing a composition for a heat dissipation member according to a twelfth aspect of the present invention includes:
A step of bonding the first inorganic filler to one end of the first silane coupling agent;
A step of bonding the second inorganic filler to one end of the second silane coupling agent;
A step of bonding the third inorganic filler to one end of the third silane coupling agent;
The composition for a heat-dissipating member contains 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 compound bonded to one end of a third silane coupling agent. A step of a third inorganic filler; and a step of bonding the other end of each of the silane coupling agents to a bifunctional or more functional polymerizable compound.
With such a configuration, a heat radiation member in which inorganic fillers are bonded to each other by a silane coupling agent and a bifunctional or more polymerizable compound can be manufactured.
[Effect of the invention]

The composition for a heat radiating member of the present invention can form a laminated body with a substrate layer such as a metal layer or a ceramic layer by curing, and has excellent substrate interlayers due to extremely high thermal conductivity and less leakage of the composition for a heat radiating member. Of adhering. Furthermore, it has excellent characteristics such as chemical stability, hardness, and mechanical strength. The laminated body of the present invention is suitable for, for example, a heat radiation substrate, a heat radiation plate (planar heat sink), a heat radiation sheet, a heat radiation coating film, a heat radiation adhesive, a heat radiation insulating substrate with an electrode, a heat conductive electronic substrate, and the like. Furthermore, the method for producing a laminated body of the present invention can more easily produce a laminated body of an organic-inorganic mixed adhesive layer and a substrate layer such as metal or ceramic with fewer steps.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that the same or similar parts are denoted by the same or similar symbols in each drawing, and repeated descriptions are omitted. The present invention is not limited to the following embodiments.

The usage of terms in this specification is as follows.
A "liquid crystal compound" and a "liquid crystal compound" are compounds exhibiting a nematic phase or a smectic liquid crystal phase.

Represented by the following one case to the meaning of - - "may be substituted with -CH = CH- other arbitrary -CH ₂ CH _2" statement like "alkyl arbitrary -CH ₂ -O- and the like may be substituted" or. For example, any of the -CH ₂ -groups substituted by -O- or -CH = CH- in C ₄ H ₉ -is C ₃ H ₇ O-, CH ₃ -O- (CH ₂ ) _2- , CH ₃ -O-CH ₂ -O- and the like. Similarly, the arbitrary -CH ₂ CH ₂ -groups substituted with -CH = CH- among C ₅ H ₁₁ -are H ₂ C = CH- (CH ₂ ) _3- , CH ₃ -CH = CH- (CH ₂ ) ₂ -etc., and further the -CH ₂ -group substituted with -O- is CH ₃ -CH = CH-CH ₂ -O- and the like. The term "arbitrary" thus means "at least one selected without distinction". Furthermore, in consideration of the stability of the compound, CH ₃ -O-CH ₂ -O-, which is not adjacent to oxygen, is preferable to CH ₃ -OO-CH _2- , which is adjacent to oxygen.

In addition, regarding ring A, the phrase "arbitrary hydrogen may be substituted by halogen, alkyl having 1 to 10 carbon atoms, or halogenated alkyl having 1 to 10 carbon atoms" means, for example, 2,4-phenylene, The aspect when at least one hydrogen at the 3,5,6 position is substituted with a substituent such as fluorine or methyl, and the aspect when the substituent is a "halogenated alkyl group having 1 to 10 carbon atoms" includes such as Examples of 2-fluoroethyl or 3-fluoro-5-chlorohexyl.

"Compound (1-1)" means a polymerizable liquid crystal compound represented by the following formula (1-1) described later, and also means at least one of the compounds represented by the following formula (1-1) . The "composition for a heat radiation member" means a composition containing at least one compound selected from the compound (1-1) or another polymerizable compound. When a compound (1-1) has multiple A's, any two A's may be the same or different. When multiple compounds (1-1) have A, any two A's may be the same or different. This rule also applies to other symbols and bases such as ^Ra or Z.

[Composition for heat dissipation member]
The composition for a 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 first inorganic filler bonded to one end of a third silane coupling agent. A tri-inorganic filler, a first di- or more-functional polymerizable compound, and a second di- or more-functional polymerizable compound, in which the first di- or more-functional polymerizable compound and the second di- or more functional polymerizable compound are used. The total ratio of 100 parts by weight of the first inorganic filler, the second inorganic filler, and the third inorganic filler is 300 parts by weight to 600 parts by weight.

The composition for a heat radiating member may include a combination of inorganic fillers capable of forming a bond between the inorganic fillers. For example, the first silane coupling agent is bonded to one end of the first silane coupling agent, and the first silane coupling agent is bonded to one end of the second silane coupling agent, and the second silane coupling agent is bonded to the first and / or second difunctional polymerizable compound. In the case of a second inorganic filler, a third inorganic filler to which a third silane coupling agent is bonded, a first bifunctional or more polymerizable compound, and a second bifunctional or more polymerizable compound, if the composition for a heat dissipating member is made If the material is hardened, the inorganic fillers can be bonded to each other via a silane coupling agent and a bifunctional or more polymerizable compound. In the case of particles using boron nitride (h-BN) as an inorganic filler, if boron nitride is treated with a silane coupling agent, boron nitride has fewer reactive groups in the plane of the particles due to its crystal structure. Therefore, only a large number of silane coupling agents are bonded around the sides. Boron nitride treated with a silane coupling agent can be bonded to a bifunctional or more polymerizable compound.
Therefore, the other end of the silane coupling agent 21 of the boron nitride 11 treated with the first silane coupling agent and the other end of the polymerizable compound 22 of the boron nitride 21 subjected to the silane coupling treatment are made of a bifunctional polymerizable compound. Bonding, whereby boron nitrides can be bonded to each other. On the other hand, in amorphous or spherical particles, such as alumina or aluminum nitride, which can be bonded to the entire surface of the silane coupling agent, the bonding is increased compared to boron nitride, and the adhesion is improved by its use. .
In this way, the first inorganic filler and the second inorganic filler are bonded to each other via a silane coupling agent and a bifunctional or more polymerizable compound to directly propagate phonons. Therefore, the cured product has extremely high thermal conductivity, and can be produced. A highly heat-dissipating member.
It is important in the present invention to achieve such a bond between the first inorganic filler and the second inorganic filler, and it is also possible to bond the silane coupling agent 22 to the first difunctional polymerizable compound 31 by using organic synthesis technology in advance. Then, the second silane coupling agent 22 is bonded to the second inorganic filler 12. By realizing the bonding between the first inorganic filler and the third inorganic filler, the adhesion with the substrate is further increased, and a heat dissipation member having high thermal conductivity can be manufactured.

[First two-functional polymerizable compound]
As the first di- or more-functional polymerizable compound, it is preferable to use a bi- or more-functional 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), has a liquid crystal skeleton and a polymerizable group, has high polymerization reactivity, a wide liquid crystal phase temperature range, and good miscibility. When this compound (1-1) is mixed with other liquid crystal compounds, polymerizable compounds, etc., it tends to become uniform.

R ^a -Z- (AZ) _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.

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

・ Terminal group R ^a
The terminal group R ^a may be a functional group that can be independently bonded to a functional group on the other end of the first silane coupling agent and the second silane coupling agent.
Examples include, but are not limited to, the polymerizable group represented by any of the following formulae (2-1) to (2-4), cyclohexene oxide, phthalic anhydride, or succinic anhydride. some.

In the formulae (2-1) to (2-2), R ^b is hydrogen, halogen, -CF ₃ , or an alkyl group having 1 to 5 carbon atoms, and q is 0 or 1. In addition, in the formulae (2-3) to (2-4), R ^c is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, or naphthalene- 2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2.2] octane-1,4-diyl, or bicyclic [3.1.0] hexane -3,6-diyl, in these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, any hydrogen may be substituted by halogen, alkyl having 1 to 10 carbon atoms Or a halogenated alkyl group having 1 to 10 carbon atoms, in the alkyl group, any -CH ₂ -may be -O-, -CO-, -COO-, -OCO-, -CH = CH-, or- C≡C- substituted. R ^{d is} each independently hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms.

Preferred examples of R ^c include 1,4-cyclohexyl, 1,4-cyclohexenyl, 2,2-difluoro-1,4-cyclohexyl, and 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, etc.

Regarding the stereo configuration of 1,4-cyclohexyl and 1,3-dioxane-2,5-diyl, trans (trans) is better than cis (cis). Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally the same, 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.

Further preferred R ^c is 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 etc. Particularly preferred R ^c is 1,4-cyclohexyl and 1,4-phenylene.

Furthermore, as a combination of the functional group which forms the bond of the terminal group Ra and ^a silane coupling agent, an oxetanyl group and an amine group, an oxetanyl group and an amine group, a vinyl group, and methacryloxy The combination of each other, a carboxyl group or a carboxylic acid anhydride residue with an amine, an imidazolyl group and an oxetanyl group, an imidazolyl group and an oxetanyl group is not limited thereto. More preferred is a combination with high heat resistance.

・ Ring structure A
When at least one ring in the ring structure A of the compound (1-1) is 1,4-phenylene, the orientation order parameter and the magnetization anisotropy are large. In addition, when at least two rings are 1,4-phenylene, the temperature range of the liquid crystal phase is wide, and the transparent point is high. When at least one hydrogen on a 1,4-phenylene ring is substituted with cyano, halogen, -CF ₃ or -OCF ₃ , the dielectric constant anisotropy is high. In addition, when at least two rings are 1,4-cyclohexyl, the transparent point is high and the viscosity is small.

As preferred A, each can be independently listed: 1,4-cyclohexyl, 1,4-cyclohexenyl, 2,2-difluoro-1,4-cyclohexyl, 1,3-di Oxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-diphenyl Fluoro-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-di Base, 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, etc.

Regarding the stereo configuration of 1,4-cyclohexyl and 1,3-dioxane-2,5-diyl, the trans is better than the cis. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally the same, 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.

Further preferred A's are each independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 so on. Particularly preferred A is 1,4-cyclohexyl and 1,4-phenylene.

・ Bond base Z
The bonding group Z in the compound (1-1) is independently a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- In the case of -CH = CH-, -CF = CF-, or-(CH ₂ ) _4- , especially a single bond,-(CH ₂ ) _2- , -CF ₂ O-, -OCF ₂ -,- When CH = CH- or-(CH ₂ ) _4- , the viscosity becomes small. In addition, 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. In addition, when the bonding group Z is an alkyl group having about 4 to 10 carbon atoms, the melting point decreases.

As the preferred Z, a single bond,-(CH ₂ ) ₂ -,-(CF ₂ ) _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C≡C-,-(CH ₂ ) ₄ -,-(CH ₂ ) ₃ O-, -O (CH ₂ ) ₃ -,-(CH ₂ ) ₂ COO-, -OCO (CH ₂ ) _2- , -CH = CH-COO-, -OCO-CH = CH-, etc.

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

The more rings the compound (1-1) has, the higher the temperature at which it is difficult to soften. Therefore, the compound (1-1) is preferred as a composition for a heat-radiating member. However, if the softening temperature becomes higher than the polymerization temperature, it is difficult to form. It is preferable to achieve a balance between the two depending on the purpose. In addition, in this specification, a six-membered ring and a condensed ring including a six-membered ring are basically regarded as a ring. For example, a three-membered ring, a four-membered ring, or a five-membered ring is not considered as a ring. A condensed 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 inert. When the compound (1-1) is optically active, the compound (1-1) has a case of having an asymmetric carbon and a case of having an asymmetric axis. The stereo configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located in either R ^a or A, and if it has an asymmetric carbon, the compatibility of the compound (1-1) is good. When the compound (1-1) has an asymmetric axis, the twist-inducing force is large. In addition, any of the optical rotation properties may be used.
As described above, by appropriately selecting terminal groups R ^a, the type of ring structure A and the bonding group Z, the number of rings, the target compound was obtained having properties.

・ Compound (1-1)
The compound (1-1) can also be represented by the following formula (1-a) or (1-b).

PY- (AZ) _m -R ^a (1-a)
PY- (AZ) _m -YP (1-b)

In (1-a) and formula (1-b), A, Z, R a and by the (1-1) defined by the formula A, Z, R ^a same meaning as the formula, P represented by the following formula ( 2-1) to the polymerizable group represented by formula (2-4), cyclohexene oxide, phthalic anhydride, or succinic anhydride, and Y independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, Preferred is an alkylene group having 1 to 10 carbon atoms. In this alkylene group, any -CH ₂ -may be -O-, -S-, -CO-, -COO-, -OCO-, or -CH = CH. -Replace. Particularly preferred Y is a single-terminal or both-terminal -CH ₂ -alkylene substituted with -O- of an alkylene group having 1 to 10 carbon atoms. m is an integer of 1 to 6, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

In the formulae (2-1) to (2-2), R ^b is hydrogen, halogen, -CF ₃ , or an alkyl group having 1 to 5 carbon atoms, and q is 0 or 1. In addition, in the formulae (2-3) to (2-4), R ^c is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, or naphthalene- 2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2.2] octane-1,4-diyl, or bicyclic [3.1.0] hexane -3,6-diyl,
In these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, and any hydrogen may be halogen, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Haloalkyl substitution,
In the alkyl group, any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-.
R ^{d is} each independently hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms.

Examples of preferred compounds (1-1) include compounds (a-1) to (a-10), compounds (b-1) to (b-16), and compound (c) shown below. -1) to compound (c-16), compound (d-1) to compound (d-15), compound (e-1) to compound (e-15), compound (f-1) to compound (f- 14) Compound (g-1) to compound (g-20). In addition, * in the formula represents an asymmetric carbon.

In these formulas, R ^a , P and Y are as defined in the 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-. Furthermore, a plurality of Z ¹ may be the same or different.

Z ^{2 is} 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 O-.

Z ^{3 is} independently a single bond, an alkyl group 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- Multiple Z ³ may be the same or different. a is an integer of 1-20.

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

A more preferable aspect of the compound (1-1) will be described. A more preferable compound (1-1) can be represented by the following formula (1-c) or (1-d).

P ¹ -Y- (AZ) _m -R ^a (1-c)
P ¹ -Y- (AZ) _m -YP ¹ (1-d)

In the formula, A, Y, Z, R a , and m are as hereinbefore defined, P ¹ represents a polymerizable group of the following formula (2-1) to formula (2-4) is represented by any one. In the case of the formula (1-d), two P ¹ represent the same polymerizable group (2-1) to polymerizable group (2-4), two Y represent the same group, and two Y are Bonded in a way that becomes symmetrical.

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

-Method for synthesizing compound (1-1) and compound (1-2) The compound (1-1) and the compound (1-2) can be synthesized by combining a known method in organic synthetic chemistry. Methods for introducing target end groups, ring structures and bonding groups into starting materials, such as Houben-Wyle (Methods of Organic Chemistry), Georg Thieme Verlag, Stuttgart), Organic Syntheses (John Wily & Sons, Inc.), Organic Reactions, John Wily & Sons Inc .)), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Lecture (Maruzen) and other books are recorded. Also, refer to Japanese Patent Laid-Open No. 2006-265527.

JX _n -J ・ ・ ・ （1-2）

In the formula (1-2), J is each independently a functional group capable of being bonded to a functional group at the other end of the formula (1-1), and X _{n is} each independently a 1,4-cyclohexyl group , 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclic [ 2.2.2] octyl-1,4-diyl, or bicyclic [3.1.0] hex-3,6-diyl, in these rings, any -CH ₂ -may be substituted by -O-, any -CH = Can be substituted by -N =, arbitrary hydrogen can be substituted by halogen, alkyl group having 1 to 10 carbon atoms, or halogenated alkyl group having 1 to 10 carbon atoms. Among the alkyl groups, any -CH ₂ -can be substituted by -O- , -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-, and n is an integer from 1 to 6.

When the bifunctional or more polymerizable compound is polycyclic, the heat resistance is increased, and when the linearity is high, the extension or fluctuation due to heat between the inorganic fillers is small, and heat phonon conduction can be efficiently transmitted. , So it is better. If it is polycyclic and has high linearity, liquid crystallinity is often exhibited as a result. Therefore, if it is liquid crystallinity, it can be said that thermal conductivity is improved.
However, the polymerizable compound having two or more functions may be a polymerizable compound that does not exhibit liquid crystallinity other than the polymerizable liquid crystal compound represented by the formula (1-1). For example, diglycidyl ether of polyether, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol, or linearity among compounds of formula (1-1) Compounds that are insufficient and do not exhibit liquid crystallinity.
The polymerizable compound can be synthesized by a method known in combination organic synthetic chemistry.

When the bifunctional or more polymerizable compound used in the present invention has a bifunctional or more functional group in order to form a bond with a silane coupling agent, it may include a trifunctional or more functional group and a tetrafunctional or more functional group. Further, it is preferable that the polymerizable compound having two or more functions has a linear bond when it has a functional group at both ends of the long side.

[Inorganic filler]
Examples of the first inorganic filler, the second inorganic filler, and the third inorganic filler include nitrides, carbides, carbon materials, metal oxides, and silicate minerals. The first inorganic filler and the third inorganic filler are preferred. They are nitride, carbide, carbon material, metal oxide, silicate mineral, and the second inorganic filler is metal oxide. The first inorganic filler, the second inorganic filler, and the third inorganic filler may be the same or different.
Specifically, examples of the first inorganic filler and the third inorganic filler include boron nitride, boron carbide, boron carbonitride, graphite, carbon fiber, and carbon nanotube as the inorganic filler having high thermal conductivity. Alternatively, alumina, silicon oxide, magnesium oxide, zinc oxide, iron oxide, ferrite, mullite, cordierite, silicon nitride, and silicon carbide can be cited. Examples of the second inorganic filler include alumina, metal nitride, zinc oxide, zirconia, and titanium oxide as the inorganic filler having high thermal conductivity.

The first inorganic filler, the second inorganic filler, and the third inorganic filler may be mixed together. Furthermore, the first inorganic filler, the second inorganic filler, and the third inorganic filler have a functional group capable of being bonded to the organic functional group of the silane coupling agent on the particle surface, and the modification amount relative to the weight of the inorganic filler is only required. It may be 0.1% 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 important, the use of insulating inorganic fillers has high reliability, such as longevity. Therefore, it is preferable not to use a carbon material as a conductor or an oxide as a part of a semiconductor.

The first inorganic filler and the third inorganic filler are more preferably boron nitride, aluminum nitride, silicon nitride, silicon carbide, graphite, carbon fiber, and carbon nanotube. Particularly preferred is hexagonal boron nitride (h-BN) or graphite. Boron nitride and graphite are preferable because the thermal conductivity in the plane direction is very high, and the dielectric constant of boron nitride is also low and the insulation is also high. For example, if plate-shaped crystal boron nitride is used, it is preferable that the plate-like structure is easily aligned along the mold due to the flow or pressure of the raw material during molding and hardening.

It is desirable that the structure of the bifunctional or more polymerizable compound has a shape and a length that allow efficient direct bonding between these inorganic fillers. The type, shape, size, and addition amount of the inorganic filler can be appropriately selected according to the purpose. When the hardened | cured material of the composition for heat radiation members requires insulation, as long as desired insulation can be maintained, it may be an inorganic filler which has electroconductivity. Examples of the shape of the inorganic filler include a plate shape, a spherical shape, an amorphous shape, a fibrous shape, a rod shape, and a cylindrical shape.

The average particle diameter of the first inorganic filler, the second inorganic filler, and the third inorganic filler is preferably from 0.1 μm to 600 μm. More preferably, it is 1 to 200 μm. When it is 0.1 μm or more, the thermal conductivity is good, and when it is 200 μm or less, the filling rate can be improved.
In addition, in this specification, an average particle diameter is a particle size distribution measurement based on the laser diffraction and scattering method. That is, using the analysis based on the Fraunhofer diffraction theory and Mie scattering theory to divide the powder from a certain particle size into two by the wet method, the large side and the small side are divided. The diameter which becomes an equivalent amount (volume basis) is set as a median particle 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 bonded to the inorganic filler used. The compound (such as boron nitride) used as the first inorganic filler, the second inorganic filler, and the third inorganic filler is preferably such that as many silane coupling agents are bonded to the reactive group as possible, so that each of the reactive groups An equal number or more of organic compounds are bonded. The reaction amount of the silane coupling agent to the inorganic filler mainly changes depending on the size of the inorganic filler or the reactivity of the silane coupling agent used. For example, the larger the inorganic filler is, the smaller the area ratio of the side surface of the inorganic filler is, so that the amount of modification is small. Although it is desired to react as many silane coupling agents as possible, if the particles are reduced, the thermal conductivity of the product will be low, so it is preferable to achieve equilibrium.

[Silane coupling agent]
As the silane coupling agent, those having a functional group capable of being bonded to each other by the silane coupling agents, those having a functional group capable of being bonded to a functional group possessed by a polymerizable compound having two or more functions, or those having a third A functional group having a functional group bonded to an inorganic filler. When the functional group on the bonding target side is an oxetanyl group, an acid anhydride residue, or the like, it is preferred to react with these functional groups, and therefore it is preferred to have an amine-based reactive group at the terminal. For example, Sila-Ace (registered trademark) S310, Sila-Ace S320, Sila-Ace S330, Sila-Ace S360, Shin-Etsu Chemical Industry Co., Ltd. KBM-903, KBE-903, etc. When the target-side terminal is an amine, a silane coupling agent having an oxetanyl group or the like at the terminal is preferred. For example, Sila-Ace (registered trademark) S510 and Sila-Ace S530 manufactured by JNC Corporation are listed.
Examples of the combination of functional groups that form a silane coupling agent and a bond on the target side include, for example, oxepropyl groups and amine groups, vinyl groups, methacryloxy groups, carboxyl or carboxylic anhydride residues, amines, and imidazoles. The group is combined with oxetrayl and the like, but is not limited to these. It is only required to be a combination of functional groups capable of forming a silane coupling agent and a target-side bond. More preferred is a combination with high heat resistance.
The first coupling agent and the second coupling agent may be the same or different.

[Other components]
The composition for a heat radiation member may include an organic compound (for example, a polymerizable compound or a polymer compound) that is not bonded by the first inorganic filler and the second inorganic filler, that is, does not contribute to the bonding, and may also include a polymerization initiator. Or solvent.
In the hardened material of the composition for a heat dissipation member, when the filler particle size is increased in order to increase the thermal conductivity, and the porosity is increased correspondingly, it can be filled with an unbonded compound. Voids can improve thermal conductivity and water vapor blocking performance.

[Unbonded polymerizable compound]
The composition for a heat radiating member may contain a polymerizable compound which is not bonded to the inorganic filler (in this case, it may not necessarily be bifunctional or more) as a constituent element. As such a polymerizable compound, a compound which does not inhibit the thermal curing of the composition for a heat radiation member and which does not evaporate or bleed out by heating is preferable. The polymerizable compound is classified into a compound having no liquid crystallinity and a compound having liquid crystallinity. Examples of the polymerizable compound having no liquid crystal properties include ethylene derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, and itaconic acid derivatives. Wait. Regarding the content, it is desirable to first prepare a composition for a heat dissipating member that does not contain an unbonded polymerizable compound, and measure the porosity to add a polymerizable compound in an amount that can fill the void.

[Unbonded polymer compound]
The composition for a heat radiating member may use a polymer compound not bonded to the inorganic filler as a constituent element. Such a polymer compound is preferably a compound that does not reduce film-forming properties and mechanical strength. The polymer compound may be a polymer compound that does not react with an inorganic filler, a silane coupling agent, and a polymerizable compound. For example, when the polymerizable compound is an oxetanyl group and the silane coupling agent has an amine group, it may be Examples include polyolefin resins, polyethylene resins, silicone resins, and waxes. Regarding the content, it is desirable to first prepare a composition for a heat dissipating member that does not contain an unbonded polymer compound, and measure the porosity thereof to add a polymer compound in an amount that can fill the void.

[Non-polymerizable liquid crystal compound]
The composition for a heat radiation member may be a liquid crystal compound which does not have a polymerizable group as a constituent element. Examples of such non-polymerizable liquid crystal compounds are the liquid crystal database (LiqCryst, LCI Press (Publisher GmbH), Hamburg, Germany, etc.) which is the date base of liquid crystal compounds. It's documented. By polymerizing the composition containing a non-polymerizable liquid crystal compound, for example, a composite material of a polymer of the compound (1-1) and a liquid crystal compound can be obtained. In such a composite material, a non-polymerizable liquid crystal compound exists in a polymer network structure such as a polymer dispersed liquid crystal. Therefore, it is desirable to have a liquid crystal compound having characteristics such as no fluidity in the temperature region used. After the inorganic filler is hardened, it is compounded by injecting voids in a temperature region showing an isotropic phase, and the inorganic filler may be mixed with a liquid crystal compound of a component calculated in advance to fill the voids. , Thereby polymerizing the inorganic fillers with each other.

[Polymerization initiator]
The composition for a heat radiating member may have a polymerization initiator as a constituent element. The polymerization initiator may be, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a thermal radical polymerization initiator, or the like depending on the constituent elements and the polymerization method of the composition. In particular, since the inorganic filler absorbs ultraviolet rays, a thermal radical polymerization initiator is preferred.
Examples of preferred initiators for thermal radical polymerization include benzamidine peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, and peroxytetracycline. Tertiary butyl valerate, di-tertiary butyl peroxide (DTBPO), tertiary butyl peroxydiisobutyrate, lauryl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), etc.

[Solvent]
The composition for a heat radiation member may contain a solvent. In the case where constituents which must be polymerized are contained in the composition, the polymerization may be performed in a solvent or may be performed without a solvent. This composition containing a solvent is applied to a substrate by, for example, a spin coat method, and then the solvent is removed and then photopolymerized. Alternatively, it may be heated to an appropriate temperature after photo-hardening, and post-treatment may be performed by thermal hardening.
Examples of preferred solvents include benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, and N-methylpyrrolidine. Ketones, dimethylformamide, dimethylmethylene, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), etc. . The solvents may be used singly or in combination of two or more kinds.
In addition, it does not make much sense to limit the use ratio of the solvent during the polymerization, as long as the efficiency of the polymerization, the cost of the solvent, and the cost of energy are taken into consideration and determined for each case.

[other]
In order to facilitate the operation, a stabilizer may be added to the composition for a heat radiation member. The stabilizer is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include antioxidants, hardeners, copper inhibitors, metal deactivators, adhesion-imparting agents, anti-aging agents, defoamers, and Static agent, weathering agent, etc. Examples of the antioxidant include hydroquinone, 4-ethoxyphenol, and 3,5-di-third-butyl-4-hydroxytoluene (BHT).
For example, when the resin forming the adhesive layer is deteriorated by contact with a metal, it is preferable to add a copper inhibitor or a metal deactivator such as those listed in Japanese Patent Laid-Open No. 5-48265.
As the copper inhibitor (trade name), Mark ZS-27 and Mark CDA-16 manufactured by ADEKA Co., Ltd. are preferred; and Mitsuko-Alber manufactured by Sanko Chemical Co., Ltd. Kelin (SANKO-EPOCLEAN); Irganox (MD1024) manufactured by BASF.
In terms of preventing deterioration of the resin in the portion of the adhesive layer that is in contact with the metal, the addition amount of the copper inhibitor is preferably 0.1% by weight relative to 100 parts by weight of the total amount of the resin contained in the adhesive layer. Parts to 3 parts by weight.
Further, additives (such as oxides) may be added in order to adjust the viscosity or color of the composition for a heat dissipation member. Examples include fine titanium oxide powder for forming white titanium oxide, carbon black for forming black carbon dioxide, and silica for adjusting viscosity. In addition, additives may be added in order to further increase the mechanical strength. Examples include inorganic fibers or cloth such as glass fiber, carbon fiber, and carbon nanotube, or polyvinyl formaldehyde, polyvinyl butyral, polyester, polyamide, and polyfluorene as polymer additives. Fiber or long molecule such as imine.

[Substrate layer]
As shown in FIG. 3, the substrate layer is bonded to an inorganic filler via a silane coupling agent and a bifunctional or more functional polymerizable compound, and constitutes a laminated body mixed with an organic-inorganic adhesive layer. Examples of the substrate layer include copper, aluminum, nickel, gold, alloys, and ceramics. For example, when a metal layer is used as the material of the substrate layer, the bond between the organic-inorganic mixed adhesion layer and the substrate layer is formed between the metal layer and the organic-inorganic mixed adhesion layer located on the outermost surface of the substrate layer. Therefore, in a material having a thin film such as plating, a bond is formed between the plating material and the organic-inorganic mixed adhesive layer through a silane coupling agent or a bifunctional or more polymerizable compound. In this way, the metal layer may be a metal that can be used as a plating material. The thickness of the substrate layer is not particularly limited, and a thickness according to the application can be used. A thicker one is preferred because it has excellent heat dissipation properties.

The substrate layer may have a shape or a material that can coat the composition for a heat dissipating member, and can be mixed with an organic-inorganic material obtained by curing the composition for a heat dissipating member and then laminated to form a laminate. Examples of the shape include a plate shape and a rod shape.
When a metal layer is used as a material of a substrate layer, it can be used not only as a heat radiation member but also as a metal electrode. Therefore, the metal layer may be a metal electrode or a metal electrode in a state where one metal electrode is divided into a plurality of pieces. That is, the metal layer may be a layer including a plurality of metal electrodes. In this way, the laminated body of the present application can also be used as an electronic substrate (printed substrate) having thermal conductivity, heat dissipation, and insulation.

[Production method]
Hereinafter, a method for producing a composition for a heat-dissipating member and a method for producing a laminated body from the composition and a substrate layer will be specifically described using the composition for a heat-dissipating member as an example.
(1) Implementing a silane coupling treatment A silane coupling treatment is performed on the first inorganic filler with a first silane coupling agent, so that the first inorganic filler and one end of the first silane coupling agent are bonded. A known method can be used for the silane coupling treatment. The second inorganic filler and the third inorganic filler can be similarly subjected to a silane coupling treatment using the second inorganic filler and the third inorganic filler.
As an example, first, an inorganic filler and a silane coupling agent are added to a solvent. Stir with a stirrer or the like and dry. After the solvent is dried, heat treatment is performed under a vacuum condition using a vacuum dryer or the like. A solvent is added to this inorganic filler, and it is pulverized by ultrasonic treatment. This solution was separated and purified using a centrifugal separator. After discarding the supernatant, a vehicle was added to perform the same operation several times. The refined inorganic filler subjected to the silane coupling treatment was dried using an oven.
(2) Modification with a bifunctional or more polymerizable compound. The second inorganic filler is subjected to a silane coupling treatment with a second silane coupling agent (or the first inorganic material subjected to the silane coupling treatment with the first silane coupling agent may be used) The filler is used as the second inorganic filler), and the first difunctional polymerizable compound and the other end of the second silane coupling agent are further bonded.
As an example, the silane coupling-treated inorganic filler is mixed with a polymer having a second or higher functionality using an agate mortar or the like, and then kneaded using a double roll or the like. Thereafter, separation and purification were performed by ultrasonic treatment and centrifugation.
(3) For example, the first inorganic filler bonded to one end of the first silane coupling agent and the second inorganic bond bonded to one end of the second silane coupling agent are weighed so that only the weight of the inorganic filler becomes 1: 1. The inorganic filler and the third inorganic filler bonded to one end of the third silane coupling agent are mixed using an agate mortar or the like. Then, they are mixed using a double roll or the like to obtain a composition for a heat radiation member.
Regarding 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 inorganic filler bonded to one end of the third silane coupling agent In the mixing ratio, when the bonding groups that form the bond between the first inorganic filler and the second inorganic filler are amine: epoxy, respectively, the weight of the inorganic filler alone is preferably 1: 0.1 to 1: 30, more preferably 1: 3 to 1:20. It is more preferably 1: 4 to 1:10. The mixing ratio is determined by the number of bonding groups that form the end of the bond between the first inorganic filler and the second inorganic filler. For example, if it is a primary amine, it can react with two oxetanyl groups. The heterocyclopropyl side may be a small amount compared with the possibility of ring opening at the oxecyclopropyl side, and therefore it is preferable to use it by increasing the amount calculated based on 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, more It is preferably in the range of 5 minutes to 1 hour. After hardening, it is preferable to perform slow cooling to suppress stress and strain. In addition, a reheating treatment may be performed to reduce strain or the like. In this manner, the formation of the organic-inorganic mixed adhesive layer and the bonding of the organic-inorganic mixed adhesive layer and the substrate layer (metal layer) can be performed by thermal compression bonding at a relatively low temperature.
In order to make the thermal conductivity in the vertical direction good, the film thickness of the organic-inorganic mixed adhesive layer is preferably thin. It is preferably 30 μm to 2000 μm, and more preferably 30 μm to 1000 μm. It is more preferably from 30 μm to 500 μm. The film thickness of the organic-inorganic mixed adhesive layer and the substrate layer (metal layer) may be appropriately changed depending on the application.

As described above, the heat radiating member of the present invention is a laminated body including an organic-inorganic mixed adhesive layer and a substrate layer (metal layer) as a cured product obtained by curing the composition for a heat radiating member. The hardened material of the composition for the heat radiation member has high thermal conductivity, and the thermal expansion coefficient is negative to positive, depending on the type of organic and inorganic materials used, the blending ratio, and hardening conditions, chemical stability, hardness, and mechanical strength. And so on. Moreover, the mechanical strength refers to Young's modulus, tensile strength, tear strength, flexural strength, flexural elastic modulus, impact strength, and the like.
The heat radiation member of the present invention can be used for a heat radiation plate, a heat radiation sheet, a heat radiation film, a heat radiation adhesive, a heat radiation molded product, and the like. Furthermore, it can be used as an electronic substrate (printed substrate) having thermal conductivity, heat dissipation, and insulation.

[Electronic equipment]
An electronic device according to the present invention includes the heat radiating member of the present invention, and an electronic device having a heat generating portion. The heat radiating member is disposed in the electronic device in contact with the heat generating portion. The aspect of the heat radiating member may be any of a heat radiating electronic substrate, a heat radiating plate, a heat radiating fin, a heat radiating film, a heat radiating adhesive, a heat radiating molded product, and the like.
For example, a semiconductor element is 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, semiconductor devices are particularly effective for power semiconductors such as silicon, silicon carbide, gallium nitride, gallium oxide, and diamond that require more efficient heat dissipation mechanisms due to high power. Examples of the electronic equipment provided with these power semiconductors include a main converter of a large power inverter, a non-stop power supply device, a variable voltage and frequency control device for an AC motor, a control device for a railway vehicle, a hybrid vehicle, Electric conveyors such as electric cars, induction heat (IH) conditioners, etc.
[Example]

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 fillers ＞
・ Boron nitride: h-BN particles, manufactured by Momentive Performance Materials Japan (combined), (brand name) PolarTherm PTX-25
・ Alumina ・ Manufactured by Japan Light Metal (stock), (brand name) Nikkei Gold FS-210B
・ Made in Japan Light Metal (stock), (brand name) Nikkei Gold FS-243
・ Made in Japan Light Metal (stock), (brand name) Nikkei Gold FS-711C
・ Made in Japan Light Metal (Stock), (brand name) Nikkei Rundum V325F
・ Producted by Japan Light Metal Co., Ltd. (brand name) Polyhedron Alumina CT50
・ Manufactured by Denka Co., Ltd. (brand name) DAW-20

＜ Silane coupling agent ＞
・ N- (2-Aminoethyl) -3-Aminopropyltrimethoxysilane, manufactured by JNC (stock), (trade name) S320



・ 3-Glycidoxypropyltrimethoxysilane, manufactured by JNC Corporation (trade name), Sila-Ace (registered trademark) S510

<Two-functional polymerizable compound>
・ Polymerizable oxelanyl compound, manufactured by JNC Corporation, with the following formula (1-11)

(1-11)
・ Polymerizable oxelanyl compound, manufactured by Mitsubishi Chemical Corporation (trade name) jER807

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



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

<Substrate layer>
A copper plate is used as a material when it is assumed to be a DCB substrate, and an aluminum plate is used as a material when it is assumed to be a DBA substrate.
・ Copper foil, manufactured by Furukawa Electric Industry Co., Ltd. (trade name) FS-WS
・ Copper plate: size 4 × 4 cm, thickness 400 μm
・ Aluminum plate: size 4 × 4 cm, thickness 400 μm

[Example 1]
・ Modified filler preparation step: 10 g of boron nitride particles (PolarTherm PTX-25 manufactured by Momentive Performance Materials Japan (KK)) as the first inorganic filler, as the first silane 1 g of Sila-Ace (registered trademark) S320 manufactured by JNC Co., Ltd. as a coupling agent was added to 100 mL of toluene, and the resulting mixture was stirred at 500 rpm for 1 hour using a stirrer. The mixture was dried at 40 ° C for 4 hours. Furthermore, after drying the solvent, a vacuum dryer set at 120 ° C. was used to perform heat treatment under vacuum for 5 hours. The obtained particles were the first inorganic filler bonded to one end of the first silane coupling agent, and this was referred to as a modified filler X.
Alumina particles (Nikkei Gold LS-210B manufactured by Nippon Light Metal Co., Ltd.) were used in place of the PTX-25, and the particles obtained in the same manner were the second inorganic bonded to one end of the second silane coupling agent The filler is referred to as a modified filler Y.
In place of the silane coupling agent S320 of the modified filler X, 2.5 g of a silane coupling agent (Sila-Ace (registered trademark) S510 manufactured by JNC) was added to 125 g of pure water The mixture was stirred at 500 rpm for 15 hours using a stirrer. Next, 12.5 g of boron nitride particles (PolarTherm PTX-25 manufactured by Momentive Performance Materials Japan Co., Ltd.) was put into the solution and stirred at 500 rpm for 1 hour using a stirrer The obtained mixture was dried at 60 ° C for 4 hours. Furthermore, after drying, it heat-processed for 5 hours under vacuum using the vacuum oven set to 80 degreeC. The obtained particles were a third inorganic filler bonded to one end of a third silane coupling agent, and this was set as a modified filler Z.

・ Production steps for the composition for heat dissipation members Weigh modified filler particles X 0.9 g, modified filler particles Y 2 g, modified filler particles Z 0.1 g, and manufactured by JNC Corporation, which is a polymer compound of the first and second functionalities. 0.6 g of compound (1-11) and 0.3 g of 4,4'-diamino-1,2-diphenylmethane which is a second difunctional or more polymerizable compound, and these are mixed at room temperature . The obtained mixture was a composition for a heat radiation member.

・ Production of the heat-dissipating member (1) 0.2 g of the composition for the heat-dissipating member was weighed and placed on a substantially lower portion (1.65 cm × 4 cm) of an aluminum plate (4 cm × 4 cm × 400 μm) as a base material, so that only The same aluminum plates were placed and held in an overlapping manner so that they were clamped, and a compression molding machine set at 150 ° C (a mini test press) (type 10 mini heating press manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. Machine) pressurize to 20 MPa, and continue heating for 15 minutes to perform alignment treatment and hardening. That is, when the composition for a heat radiating member is expanded between aluminum plates, since the boron nitride particles are plate-like particles, the boron nitride particles are aligned parallel to the aluminum plate. In addition, the amount of the composition for a heat-dissipating member was adjusted so that the thickness of the layer of the aluminum plate / the composition for a heat-dissipating member / the laminated body of the aluminum plate became about 1 mm. The obtained laminated body was made into a heat radiation member (1).

・ Production of the heat-dissipating member (2) 0.1 g of the composition for the heat-dissipating member was weighed, placed on a copper foil (5 cm × 5 cm × 35 μm) as a base material, and the same copper foil was placed in an overlapping manner. Clamp, press to a temperature of 20 MPa using a compression molding machine (mini test press-10 small heating press manufactured by Toyo Seiki Seisakusho Co., Ltd.) set to 150 ° C, and heat it up For 15 minutes, alignment treatment and hardening are performed. That is, when the composition for a heat radiation member is expanded between copper foils, since the boron nitride particles are plate-like particles, the boron nitride particles are aligned parallel to the copper foil. In addition, the amount of the composition for a heat-dissipating member was adjusted so that the thickness of the layer of the copper foil / composition for a heat-dissipating member / layer of the copper foil became approximately 300 μm. The obtained laminated body was made into a heat radiation member (2).

＜ Evaluation of leakage degree of subsequent members (leak rate) ＞
Generally, when a mixture is applied under pressure using a mixture of a resin component such as a polymerizable compound and an inorganic filler, the inorganic filler component remains between the adherends, causing an excessive resin component to leak out to the periphery. . However, by adopting the structure of FIG. 1 of the present invention, the problem of separation of the resin component from the inorganic filler can be solved. On the contrary, it is considered that the case where there is little resin component leaked is achieved by the structure of FIG. 1.
The degree of leakage of the adhering member was confirmed as follows.
In the heat radiating member (1), a value obtained by dividing the area leaked out as shown in FIG. 6 by the area to be followed multiplied by 100 was calculated as the leakage rate.
＜ Measurement of peeling strength ＞
The tensile test was performed as follows, and the peeling strength was confirmed.
In the heat dissipation member (1), as shown in Figs. 4 and 5, two unattached portions of the aluminum plate were clamped up and down using a tensile tester (AGS-X square tensile test manufactured by Shimadzu Corporation). Machine), stretched at a speed of 5 mm / min, and measured the tension at break. If it is not broken, the detection limit (1000 N) or more.
<Measurement of thermal diffusivity>
The heat diffusivity was measured using a heat dissipating member (2) by an ai-phase mobile 1u thermal diffusivity device manufactured by ai-phase (strand).

[Example 2]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylidene diphenylamine is used as the second difunctional or more polymerizable compound. Except for this, production and evaluation were performed in the same manner as in Example 1.

[Example 3]
Instead of Nikkei Gold LS-210B, Nikkei Gold LS-243 was used as the second inorganic filler. Except for this, production and evaluation were performed in the same manner as in Example 1.

[Example 4]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylidene diphenylamine is used as the second difunctional or more polymerizable compound. Except for this, production and evaluation were performed in the same manner as in Example 3.

[Example 5]
Instead of Nikkei Gold LS-210B, Nikkei Gold LS-711C was used as the second inorganic filler. Except for this, production and evaluation were performed in the same manner as in Example 1.

[Example 6]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylidene diphenylamine is used as the second difunctional or more polymerizable compound. Except for this, production and evaluation were performed in the same manner as in Example 5.

[Example 7]
Instead of Nikkei Gold LS-210B, Nikkei Rundum V325F was used as the second inorganic filler. Except for this, production and evaluation were performed in the same manner as in Example 1.

[Example 8]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylidene diphenylamine is used as the second difunctional or more polymerizable compound. Except for this, production and evaluation were performed in the same manner as in Example 7.

[Example 9]
Polyhedron alumina CT50 was used instead of Nikkei Gold LS-210B. Except for this, production and evaluation were performed in the same manner as in Example 1.

[Example 10]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylidene diphenylamine is used as the second difunctional or more polymerizable compound. Except for this, production and evaluation were performed in the same manner as in Example 9.

[Example 11]
Use DAW-20 instead of Nikkei Gold LS-210B. Except for this, production and evaluation were performed in the same manner as in Example 1.

[Example 12]
Instead of 4,4'-diamino-1,2-diphenylmethane, 4,4'-ethylidene diphenylamine is used as the second difunctional or more polymerizable compound. Except for this, production and evaluation were performed in the same manner as in Example 11.

[Comparative Example 1]
Epikote jER807 was used in place of the compound (1-11) manufactured by Genesis. Except for this, production and evaluation were performed in the same manner as in Example 11.

The evaluation results of the examples and comparative examples are shown in Table 1.
Moreover, the composition of the composition for heat radiation members of an Example and a comparative example is shown in Table 2.

[Table 1]

[Table 2]

As shown in Table 1 above, when the compound (1-11) manufactured by Genesis Corporation is used as the first difunctional polymerizable compound, the adhesiveness with the metal layer as the substrate layer is high. Leakage of the composition for a heat radiating member is also small, and the thermal diffusivity in a vertical direction becomes a high value. In particular, when 4,4'-ethylenediphenylamine having an amine group is used, the adhesiveness is good.
In contrast, in the case of using Epikote jER807, which is a polymerizable oxetanyl compound, as the first di- or more functional polymerizable compound, leakage of the composition for a heat-dissipating member is significant and severely affected. This affects poor adhesion to the metal layer as the substrate layer, and also has a low thermal diffusivity.

1‧‧‧ substrate

10‧‧‧ inorganic filler

11‧‧‧The first inorganic filler / boron nitride

12‧‧‧Second inorganic filler

13‧‧‧Third inorganic filler

21‧‧‧first silane coupling agent / first coupling agent / silane coupling agent

22‧‧‧Second Silane Coupling Agent / Second Coupling Agent / Silane Coupling Agent

23‧‧‧Third Silane Coupling Agent

31‧‧‧The first two-functional polymerizable compound

32‧‧‧Second bi-functional polymerizable compound

41‧‧‧ metal plate above

42‧‧‧Composition for heat dissipation member

43‧‧‧ metal plate below

51‧‧‧ Fitting surface

52‧‧‧Composition for heat dissipation member leaking from bonding surface

61‧‧‧ Area to be continued

62‧‧‧ Leaked Area

FIG. 1 is a conceptual diagram showing a state in which 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.

FIG. 2 shows that the inorganic filler 10 bonded to one end of the second coupling agent 22 is polymerized via the first bifunctional or higher polymerizable compound 31 and the second bifunctional or higher polymerizable compound 32, and is further polymerized via the first or second functional group. Conceptual view of the case where the chemical compound 31 is bonded to the substrate 1.

FIG. 3 is a conceptual diagram showing a case where the first inorganic filler 11 bonded to one end of the first coupling agent 21 and the one end bonded to the second silane coupling agent 22 are hardened by the hardening treatment of the composition for a heat sink member. The second inorganic filler 12 is bonded via the first bi-functional polymerizable compound 31 and / or the second bi-functional polymerizable compound 32, and the second inorganic filler 12 is bonded to the substrate 1 and the second silane coupling agent 22 The second bi- or more-functional polymerizable compound 31 bonded at one end is further bonded through the first bi- or more-functional polymerizable compound 31, the second bi- or more-functional polymerizable compound 32, and the first bi- or more-functional polymerizable compound. The first inorganic filler 11 bonded to one end of the first silane coupling agent 21 and the third inorganic filler 13 bonded to one end of the third silane coupling 23 are The other end of the one silane coupling agent 21 is bonded to the other end of the third silane coupling agent 23 and is polymerizable through the second difunctionality through the third silane coupling agent 23 bonded to the third inorganic filler 11. Compound 32 and the first difunctional polyfunctional Compound 31 and the substrate 1 is bonded to the case.

FIG. 4 is a diagram showing a test member used in a tensile test and a leak rate measurement.

FIG. 5 is a view showing a cross section of a test member used in a tensile test and a leak rate measurement.

FIG. 6 is a diagram showing an upper surface of a test member used in the leak rate measurement.

Claims (12)

A composition for a heat dissipation member, comprising: 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 bonded to a third silane coupling agent. The third inorganic filler, the first di- or more-functional polymerizable compound, and the second di- or more-functional polymerizable compound, in the composition for a heat dissipation member, The first inorganic filler, the second inorganic filler, and the 100% by weight of the total amount of the first bifunctional or more polymerizable compound and the second bifunctional or more polymerizable compound The ratio of the total amount of the third inorganic filler is 300 parts by weight to 600 parts by weight. The composition for a heat-dissipating member according to item 1 of the scope of patent application, wherein the first inorganic filler and the second inorganic filler use the other end of the silane coupling agent bonded to each other, and are selected from the first At least one of the bifunctional or more polymerizable compound and the second bifunctional or more polymerizable compound are bonded. The composition for a heat dissipating member according to item 1 or 2 of the scope of the patent application, wherein the first or second functional polymerizable compound or the second or more functional polymerizable compound contains a compound selected from the following formula (1 -1) and at least two of the group consisting of the polymerizable liquid crystal compound represented by the following formula (1-2): R ^a -Z- (AZ) _m -R ^a (1-1) In (1-1), R ^{a is} independently a functional group capable of being bonded to a functional group at the other end of the silane coupling agent, and A is independently 1,4-cyclohexyl and 1,4-cyclohexyl Alkenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1, 4-diyl or bicyclic [3.1.0] hex-3,6-diyl, in these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, any Hydrogen may be substituted by halogen, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. In the alkyl group, any -CH ₂ -may be -O-, -CO-, -COO- , -OCO-, -CH = CH-, or -C≡C-, Z is independently a single bond or an alkylene group having 1 to 20 carbon atoms. Among the alkylene groups, any -CH ₂ -Can be -O-, -S-, -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-,- N = N-, -N (O) = N-, or -C≡C- substitution, arbitrary hydrogen may be substituted by halogen, m is an integer of 1 to 6, JX _n -J (1-2), the formula ( In 1-2), J is each independently a functional group capable of bonding to the functional group at the other end of the formula (1-1), and X is each independently 1,4-cyclohexyl, 1,4- Cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octyl -1,4-diyl, or bicyclic [3.1.0] hex-3,6-diyl, in these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be -N = Substituting, arbitrary hydrogen may be substituted by halogen, alkyl group having 1 to 10 carbon atoms, or halogenated alkyl group having 1 to 10 carbon atoms. In the alkyl group, any -CH ₂ -may be -O-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-, and n is an integer of 1 to 6. The composition for a heat radiating member according to item 3 of the scope of patent application, wherein 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 -, Said a is an integer of 1-20. The composition for a heat dissipation member according to item 3 or 4 of the scope of patent application, wherein in the formula (1-1), R ^{a is} independently the following formula (2-1) to formula (2- 4) the polymerizable group represented by any one, In the formulae (2-1) to (2-2), R ^b is hydrogen, halogen, -CF ₃ , an alkyl group having 1 to 5 carbon atoms, and q is 0 or 1; ) To formula (2-4), R ^c is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenyl, naphthalene-2,6-diyl, tetrahydro Naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2.2] octane-1,4-diyl, or bicyclic [3.1.0] hex-3,6-diyl, the In these rings, any -CH ₂ -may be substituted by -O-, any -CH = may be substituted by -N =, and any hydrogen may be halogenated, alkyl group having 1 to 10 carbon atoms, or halogenation having 1 to 10 carbon atoms. Alkyl substitution, in the alkyl, any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH = CH-, or -C≡C-; R ^d respectively It is independently hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms. The composition for a heat dissipation member according to any one of claims 1 to 5 in the scope of patent application, wherein 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 same as the first inorganic filler. The composition for a heat dissipation member according to item 6 of the scope of patent application, wherein The first inorganic filler is at least one selected from the group consisting of boron nitride, aluminum nitride, boron carbide, boron carbonitride, graphite, carbon fiber, carbon nanotube, alumina, and cordierite, and the second inorganic filler The filler is at least one selected from the group consisting of aluminum oxide, metal nitride, zinc oxide, zirconia, and titanium oxide. The composition for a heat dissipating member according to any one of claims 1 to 7, wherein a modification rate of the silane coupling agent of the first inorganic filler is 0.1% by weight or more. The composition for a heat dissipation member according to any one of claims 1 to 8 of the scope of patent application, It further includes a polymerizable compound that is not bonded by the first inorganic filler and the second inorganic filler. A heat radiating member comprising the hardened body of the composition for a heat radiating member according to any one of claims 1 to 9 and a substrate layer. An electronic machine including: A heat dissipation member as described in item 10 of the scope of patent application; and Electronic device with heating part, The heat radiating member is disposed in the electronic device in contact with the heat generating portion. A manufacturing method of a composition for a heat dissipation member includes: A step of bonding the first inorganic filler to one end of the first silane coupling agent; A step of bonding the second inorganic filler to one end of the second silane coupling agent; A step of bonding the third inorganic filler to one end of the third silane coupling agent; The composition for a heat-dissipating member contains 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 A step of a third inorganic filler; and A step of bonding the other end of each of the silane coupling agents to a bifunctional or more functional polymerizable compound.