TW201842151A - Resin composition for heat dissipation member, heat dissipation member, electronic device, manufacturing method of the heat dissipation member - Google Patents

Abstract

The present invention is a composition which is capable of forming a heat dissipation member that has high thermal conductivity and high heat resistance, while being able to be controlled with respect to the thermal expansion coefficient. A composition for heat dissipation members according to the present invention contains: a heat conductive first inorganic filler 1 which is bonded to one end of a first coupling agent; and a heat conductive second inorganic filler 2 which is bonded to one end of a second coupling agent, with the other end of the second coupling agent being bonded with a bi- or higher functional polymerizable compound 22. The bi- or higher functional polymerizable compound is a non-liquid crystalline compound; and at least one functional group of the polymerizable compound is able to be bonded to the other end of the first coupling agent.

Description

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

The present invention relates to a composition for a heat radiation member. In particular, the present invention relates to a composition for a heat radiation member that can form a heat radiation member that can efficiently dissipate heat by conducting and transmitting heat generated inside an electronic device and can control the thermal expansion coefficient.

In recent years, in semiconductor devices for power control such as hybrid vehicles or electric automobiles, or central processing units (CPUs) for high speed computers, etc., A high thermal conductivity of the package material is desired without increasing the temperature of the semiconductor inside. That is, the ability to efficiently release heat generated from a semiconductor chip to the outside becomes important. In addition, as the operating temperature increases, thermal strain occurs due to a difference in thermal expansion coefficient between materials used in the package, and a reduction in life due to peeling of the wiring or the like becomes a problem.

As a method of solving such a heat radiation problem, the method of contacting a highly thermally-conductive material (heat radiation member) with a heat-generating part, and taking out heat to the outside can be mentioned. Patent Literature 1 discloses a heat-radiating member which is a heat-radiating member obtained by compounding an organic material and an inorganic material, and which connects the inorganic materials with a coupling agent and a polymerizable liquid crystal compound (paragraph 0007, FIG. 1, and FIG. 2). . By coupling the polymerizable liquid crystal compound with a coupling agent, the thermal conductivity between the inorganic materials can be extremely improved. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2016/031888

[Problems to be Solved by the Invention] However, liquid crystal compounds have a large number of reaction sites and are easily affected by heat. Therefore, an object of the present invention is to provide a composition and a heat radiation member that can form a heat radiation member that has high thermal conductivity, can control the thermal expansion coefficient, and further has high heat resistance. [Means for solving problems]

The present inventors have found that if a polymer having a specific structure among polymerizable compounds and coupling agents is used in a composition for a heat release member, the polymer has high thermal conductivity, can control the thermal expansion rate, and can further improve heat resistance. invention.

As shown in FIG. 2, the composition for a heat radiation member according to the first aspect of the present invention includes, for example, a first inorganic filler 1 having thermal conductivity bonded to one end of the first coupling agent 11, and a second coupling agent 12. A second thermally conductive second inorganic filler 2 bonded to one end thereof, and a second inorganic filler having a difunctional or more functional polymerizable compound 22 bonded to the other end of the second coupling agent 12, and the second coupling agent A polymerizable compound represented by the following formula (1-1) is bonded to 12 as the difunctional or more functional polymerizable compound 22, the polymerizable compound 22 is a non-liquid crystal compound, and the polymerizable compound 22 has At least one of the functional groups may be bonded to the other end of the first coupling agent 11. R ^a -R ⁶ -O- (Rx) _n -OR ¹¹ -R ^a (1-1) In the formula (1-1), R ^a is the following formula (2-1) to formula (2- 2), an amine group, a vinyl group, a carboxylic acid anhydride residue, or any polymerizable group containing these structures; Rx is any one of the following formulae (2-3) to (2-6); n is An integer of 1 to 3; R ⁶ and R ¹¹ are each independently a single bond or an alkylene group having 1 to 20 carbon atoms. [Chemical 1] 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. [Chemical 2] In the formulae (2-4) to (2-6), R ⁷ to R ¹⁰ are each independently hydrogen or an alkylene group having 1 to 20 carbon atoms. The so-called "one end" and "the other end" may be the edges or ends of the 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, the inorganic filler can be directly bonded to each other via the coupling agent and the polymerizable compound, thereby forming a heat radiation member. Therefore, a phonon, which is a main element of heat conduction, can be directly transmitted, and the heat-radiated member after curing can have extremely high heat conductivity not only in the horizontal direction but also in the thickness direction. Furthermore, since the structure of the polymerizable compound has few reaction sites and is not easily affected by heat, the exothermic member can have high heat resistance.

The composition for a heat radiation member according to a second aspect of the present invention is the composition for a heat radiation member according to the first aspect of the present invention, which is bonded to the first inorganic filler and the second inorganic filler. The silane coupling agent represented by the following formula (3-1) is a composition of the first coupling agent and the second coupling agent. (R ¹ -O) _j -Si (R ⁵ ) _3-j- (R ² ) _k- (R ³ ) _k- (R ⁴ ) _k -Ry (3-1) In the formula (3-1), , R ¹ is H-, or CH _3- (CH ₂ ) _{0 to 4-} ; R ² is-(CH ₂ ) _{0 to 3} -O-; R ³ is 1,3-phenylene, 1,4- Phenylene, naphthalene-2,6-diyl, or naphthalene-2,7-diyl; R ⁴ is-(NH) _{0 to 1-} (CH ₂ ) _{0 to 3-} ; R ⁵ is H-, or CH _3- (CH ₂ ) _{0 to 7-} ; Ry is oxetanyl, oxetanyl, amino, vinyl, carboxylic anhydride residue, or any polymerizable group containing these structures; j Is an integer of 0 to 3; k is an integer of 0 to 1; Formula (3-1) includes at least one of R ³ and R ⁴ . If comprised in this way, since the structure of a coupling agent has few reaction sites and is not easily affected by heat, a heat release member can have high heat resistance.

The composition for a heat radiation member according to a third aspect of the present invention is the composition for a heat radiation member according to the first aspect or the second aspect of the present invention, wherein the first inorganic filler and the second inorganic filler Respectively selected from boron nitride, boron carbide, boron carbonitride, graphite, carbon fiber, carbon nanotube, graphene, alumina, aluminum nitride, silicon dioxide, silicon nitride, silicon carbide, and oxide At least one of zinc, magnesium oxide, magnesium hydroxide, cordierite, or iron oxide-based materials. With such a structure, the thermal conductivity of the inorganic filler is high, and the thermal expansion coefficient is positive or very small, or negative. By compounding with these fillers, the target composition for an exothermic member can be obtained.

The composition for a heat radiation member according to a fourth aspect of the present invention is the composition for a heat radiation member according to any one of the first aspect to the third aspect of the present invention, and further includes a component having the same properties as the first aspect. A third inorganic filler having a different thermal expansion coefficient from the inorganic filler and the second inorganic filler. With such a configuration, when the first inorganic filler and the second inorganic filler have different thermal expansion coefficients, if these are compounded, the thermal expansion coefficient of the composite composition for an exothermic member is only The median value when each filler is compounded. However, in this state, when there are many gaps in the filler, not only does the thermal conductivity not increase, but also the electrical insulation decreases due to the penetration of moisture into the gaps. Therefore, by adding a third inorganic filler having a high thermal conductivity and a smaller particle diameter than the first inorganic filler and the second inorganic filler, the gaps between the first inorganic filler and the second inorganic filler are filled, and the material is improved. stability. Furthermore, compared with a case where only the first inorganic filler and the second inorganic filler are used, the addition of the third inorganic filler having a higher thermal conductivity can increase the thermal conductivity of the heat releasing member. The inorganic filler used in the third inorganic filler is not restricted. When high insulation is required, boron nitride or aluminum nitride, silicon carbide, and silicon nitride are desirable. When high insulation is not required. Below, ideally, those with high thermal conductivity such as diamond, carbon nanotubes, graphene, and metal powder.

The composition for a heat radiation member according to a fifth aspect of the present invention is the composition for a heat radiation member according to any one of the first aspect to the fourth aspect of the present invention, and further includes: the first inorganic An organic compound or a polymer compound to which the filler and the second inorganic filler are not bonded. With such a structure, in a heat-radiating member in which the first inorganic filler and the second inorganic filler are connected and hardened, as the particle diameter of the filler is increased in order to increase the thermal conductivity, the porosity is increased accordingly. In this case, the gap can be filled with an unbonded compound, and thermal conductivity, water vapor blocking performance, and the like can be improved.

A sixth aspect of the present invention is a heat release member, which is a heat release member in which the composition for any one of the first to fifth aspects of the present invention is cured. With such a structure, the exothermic member has a bond between the inorganic fillers, and can have extremely high thermal conductivity and heat resistance.

An electronic device according to a seventh aspect of the present invention includes the heat radiation member according to the sixth aspect of the present invention; and an electronic device having a heat generation portion, and the heat radiation member is disposed in contact with the heat generation portion. The electronic device. With such a configuration, the heat generated in the electronic device can be efficiently conducted by the heat radiation member having high thermal conductivity and high heat resistance. In addition, by making the thermal expansion coefficient in the plane direction close to the thermal expansion coefficient of a copper wiring or a semiconductor element such as silicon or silicon nitride mounted on a heat radiation member, it is possible to suppress spalling due to thermal cycling.

As shown in FIG. 2, for example, a method for manufacturing an exothermic member according to the eighth aspect of the present invention includes a step of bonding a thermally conductive first inorganic filler 1 and one end of a first coupling agent 11; and a thermally conductive second A step of bonding the inorganic filler 2 to one end of the second coupling agent 12; a step of bonding the other end of the second coupling agent 12 to a difunctional or more functional polymerizable compound 22; and a step of bonding the first coupling agent 11 A step of bonding the other end to the difunctional or more functional polymerizable compound 11 and the difunctional or more functional polymerizable compound 22 is a polymerizable compound represented by the following formula (1-1). The compound is a non-liquid crystalline compound. R ^a -R ⁶ -O- (Rx) _n -OR ¹¹ -R ^a (1-1) In the formula (1-1), R ^a is the following formula (2-1) to formula (2- 2), an amine group, a vinyl group, a carboxylic acid anhydride residue, or any polymerizable group containing these structures; Rx is any one of the following formulae (2-3) to (2-6); n is An integer of 1 to 3; R ⁶ and R ¹¹ are each independently a single bond or an alkylene group having 1 to 20 carbon atoms. [Chemical 3] 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. [Chemical 4] In the formulae (2-4) to (2-6), R ⁷ to R ¹⁰ are each independently hydrogen or an alkylene group having 1 to 20 carbon atoms. With such a structure, it is possible to produce a heat releasing member including an inorganic filler in which inorganic fillers are bonded to each other via a coupling agent and a polymerizable compound, and a heat releasing member having high heat resistance. [Effect of the invention]

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

This application is based on Japanese Patent Application No. 2017-072255 filed in Japan on March 31, 2017, and its content forms part of the content of this application. The present invention can be more fully understood from the following detailed description. The further application range of this invention will become clear by the following detailed description. However, the detailed description and specific examples are ideal embodiments of the present invention, and are described only for explanation. Based on the detailed description, those skilled in the art will recognize various changes and modifications within the spirit and scope of the present invention. The applicant does not intend to present the described implementation forms to the public, and those who change or replace the language in the case that may not be included in the scope of the patent application for the invention are also made part of the invention under the equality theory.

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 by 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. The "polymerizable group" is a group participating in a polymerization reaction.

The meanings of terms such as "arbitrary -CH ₂ -in the alkyl group may be substituted with -O-, etc." or "arbitrary -CH ₂ CH ₂ -may be substituted with -CH = CH-, etc." 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, any of the -CH ₂ CH ₂ -groups substituted with -CH = CH- in C ₅ H ₁₁ -is H ₂ C = CH- (CH ₂ ) _3- , CH ₃ -CH = CH- (CH ₂ ) ₂ -etc., And further any -CH ₂ -substituted by -O- is CH ₃ -CH = CH-CH ₂ -O- or the like. As such, the term "arbitrary" means "at least one selected without distinction". Furthermore, considering the stability of the compound, CH ₃ -O-CH ₂ -O-, which is not adjacent to oxygen, is preferred to CH ₃ -OO-CH _2- , which is adjacent to oxygen.

In addition, with regard to ring A, the term "arbitrary hydrogen may be substituted with halogen, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms" means, for example, 2,4-phenylene In the case where at least one hydrogen at the 3, 5, 6 position is substituted with a substituent such as fluorine or methyl, the embodiment in which the substituent is a "halogenated alkyl group having 1 to 10 carbon atoms" includes Examples are 2-fluoroethyl or 3-fluoro-5-chlorohexyl.

"Compound (1-2)" means the liquid crystal compound represented by the following formula (1-2) mentioned later, and may mean at least one of the compounds represented by the following formula (1-2). The "composition for an exothermic member" means a composition containing at least one compound selected from the compound (1-2) or another polymerizable compound. When a compound (1-2) has multiple A's, any two A's may be the same or different. When multiple compounds (1-2) 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 Exothermic Member] The composition for an exothermic member of the present application is a composition that forms an exothermic member by bonding inorganic fillers to each other via a coupling agent and a difunctional polymerizable compound or more by curing. FIG. 1 is an example in the case of using boron nitride as an inorganic filler. If boron nitride (h-BN) is treated with a coupling agent, in the case of boron nitride, since there is no reactive group on the plane of the particle, the coupling agent is bonded only around the particle. The coupling agent-treated boron nitride can form a bond with a polymerizable compound. Therefore, as shown in FIG. 2, the other end of the coupling agent 11 of the boron nitride 1 subjected to the coupling treatment and the polymerizable compound 22 of the boron nitride 2 which has been subjected to the coupling treatment and further modified by the polymerizable compound 22 are used. The other end is bonded, whereby the boron nitrides can be bonded to each other as shown in FIG. 1. In this way, by bonding inorganic fillers to each other via a coupling agent and a polymerizable compound, phonons can be directly propagated. Therefore, the heat-generating member after curing has extremely high thermal conductivity, and an organic material that directly reflects the thermal expansion coefficient of the inorganic component can be produced Inorganic composite materials.

The composition for a heat radiation member according to the first embodiment of the present invention includes, for example, as shown in FIGS. 1 and 2, a plurality of thermally conductive first inorganic fillers 11 bonded to one end of the first coupling agent 1; The second inorganic filler 2 is a thermally conductive second inorganic filler 2 bonded to one end of the second coupling agent 12, and a second inorganic filler having a difunctional or higher functional polymerizable compound 22 is further bonded to the other end of the second coupling agent 12. As shown in FIG. 2, when the composition for an exothermic member is cured, the other end of the coupling agent 11 bonded to the first inorganic filler 1 is bonded to the polymerizable compound 22 of the second inorganic filler 2. In this way, bonds between the inorganic fillers are formed.

[Difunctional or More Polymerizable Compound] The difunctional or more polymerizable compound may be a non-liquid crystalline compound. The bifunctional or more polymerizable compound has a functional group capable of forming a bond with a coupling agent. Examples of the difunctional or more polymerizable compound include a polymerizable compound represented by the following formula (1-1). R ^a -R ⁶ -O- (Rx) _n -OR ¹¹ -R ^a (1-1) In the formula (1-1), R ^a is the following formula (2-1) to formula (2- 2), an amino group, a vinyl group, a carboxylic anhydride residue, or any polymerizable group containing these structures; Rx is a naphthalene-2,6-diyl group, or the following formulae (2-3) to (2) -6) Any of naphthalene-2,7-diyl, biphenyl-2,2 ', biphenyl-2,4', and biphenyl-3,3 '; n is 1 to An integer of 3; R ⁶ and R ¹¹ are each independently a single bond or an alkylene group having 1 to 20 carbon atoms. [Chemical 5] 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. [Chemical 6] In the formulae (2-4) to (2-6), R ⁷ to R ¹⁰ are each independently hydrogen or an alkylene group having 1 to 20 carbon atoms.

In addition, R ^a may be a functional group which can be independently bonded to a functional group on the other end of the first coupling agent and a functional group on the other end of the second coupling agent, respectively. For example, cyclohexene oxide, phthalic anhydride, or succinic anhydride is mentioned besides the polymerizable group represented by said Formula (2-1)-Formula (2-2), However, It is not limited to these. Examples of the combination of functional groups that form ^a bond between R ^a and a coupling agent include oxepropyl and amine, vinyl, methacryloxy, carboxyl or carboxylic anhydride residues, amines, and imidazoles Combinations such as oxetanyl are not limited thereto. What is necessary is just the combination of the functional group which can form the bond of a polymerizable compound and a coupling agent. More preferred is a combination with high heat resistance.

The polymerizable compound represented by formula (1-1) has few reaction sites in the structure and is not easily affected by heat. On the other hand, it was found that the phonon of the structure has excellent propagation. Therefore, the heat radiation member formed from the composition for a heat radiation member can have high thermal conductivity and can have high heat resistance.

The difunctional or more polymerizable compound may be a liquid crystal compound. Examples of the difunctional or more polymerizable compound having liquid crystallinity include a polymerizable liquid crystal compound represented by the following formula (1-2). The polymerizable liquid crystal compound has a liquid crystal skeleton and a polymerizable group, and has high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, and the like. When this compound (1-2) is mixed with other liquid crystal compounds, polymerizable compounds, etc., it becomes easy to become uniform. R ^a -Z- (AZ) _m -R ^a (1-2)

By suitably selecting the compound (1-2) of the terminal group R ^a, ring structure A and the bonding group Z, can arbitrarily adjust the liquid crystal phase exhibits properties like region. 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 (1-2), and preferable examples thereof will be described below.

• Terminal group R ^{a The} terminal group R ^a has the same meaning as that defined for R ^a in the formula (1-1).

Ring structure A In the case where at least one ring in ring structure A of the compound (1-2) 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 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, 1,4-cyclohexyl, 1,4-cyclohexenyl, 2,2-difluoro-1,4-cyclohexyl, 1,3-dioxane- 2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1 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.

The stereo configuration of 1,4-cyclohexyl and 1,3-dioxane-2,5-diyl is the trans configuration is better than the cis configuration. The structures of 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are the same, so the latter is not exemplified. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

Further preferred A 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 Phenyl etc. Particularly preferred A is 1,4-cyclohexyl and 1,4-phenylene.

Bonding group Z The bonding group Z to the compound (1-2) is a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, or-(CH ₂ ) ₄ -especially single bonds,-(CH ₂ ) _2- , -CF ₂ O-, -OCF _2- When -CH = CH- or-(CH ₂ ) _4- , the viscosity becomes small. When the bonding group Z is -CH = CH-, -CH = N-, -N = CH-, -N = N-, or -CF = CF-, the temperature range of the liquid crystal phase is wide. When the bonding group Z is an alkyl group having about 4 to 10 carbon atoms, the melting point is lowered.

Examples of preferred Z include 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.

Further preferred Z include 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 a single bond,-(CH ₂ ) _2- , -COO-, or -OCO-.

The more the compound (1-2) has a larger number of rings, the more difficult it is to soften at a higher temperature. Therefore, it is preferable as an exothermic material. However, if the softening temperature becomes higher than the polymerization temperature, it is difficult to form, so It is better to strike a balance between the two according to 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 or a four-membered ring and a five-membered ring are not considered as a ring. A condensed ring such as a naphthalene ring or a fluorene ring is regarded as one ring.

The compound (1-2) may be optically active or optically inert. When the compound (1-2) is optically active, the compound (1-2) 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. If the asymmetric carbon is present, the compatibility of the compound (1-2) is good. In the case where the compound (1-2) 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 the terminal group R ^a, ring structure A and the type of bonding group Z, the number of rings, the compound having desired physical properties can be obtained.

Compound (1-2) The compound (1-2) 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)

The formula (1-a) and formula (1-b), the defined ^A, Z, R ^a in the formula (1-2) A, Z, R a is the same meaning, P represented by the following formula (2-1) to the polymerizable group represented by formula (2-2), cyclohexene oxide, phthalic anhydride, or succinic anhydride, Y represents a single bond or an alkylene group having 1 to 20 carbon atoms, and Preferred is an alkylene group having 1 to 10 carbon atoms. In this alkylene group, any -CH ₂ -may pass through -O-, -S-, -CO-, -COO-, -OCO-, or -CH = CH. -Replace. Particularly preferred Y is a single-terminal or both-terminal -CH ₂ -O-substituted 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. [Chemical 7] 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.

Examples of preferred compounds (1-2) 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.

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

In the chemical formulas (a-1) to (g-20), 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-, The plurality of Z ³ may be the same or different. a is an integer of 1-20.

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

A more preferable aspect of the compound (1-2) will be described. A more preferable compound (1-2) can be represented by the following formula (1-c) or (1-d). P ¹ -Y- (AZ) _m -R ^a (1-c) P ¹ -Y- (AZ) _m -YP ¹ (1-d) In the formula, A, Y, Z, R ^a and m are as above As defined herein, P ¹ represents a polymerizable group represented by the following formula (2-1) to formula (2-2). In the case of the formula (1-d), two P ¹ represent the same polymerizable group (2-1) to polymerizable group (2-2), two Y represent the same group, and two Y are Bonded in a way that becomes symmetrical. [Chemical 22]

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

[Chemical 23]

[Chemical 24]

[Chemical 25]

-Method for synthesizing compound (1-1) (1-2) The compound (1-1) (1-2) can be synthesized by a combination of methods known in organic synthetic chemistry. Methods for introducing target terminal 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.

The difunctional or more functional polymerizable compound (hereinafter, simply referred to as “polymerizable compound”) may be a polymerizable compound other than the polymerizable compound represented by the formula (1-1) (1-2). 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 (1-2) 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.

In order to form a bond with a coupling agent, the polymerizable compound used in the present invention preferably has a difunctional or higher functional group, and contains a trifunctional or higher functional group or a tetrafunctional or higher functional group. Furthermore, a compound having a functional group at both ends of the long side of the polymerizable compound is preferable because it can form a linear bond. In addition, when the surface modification by a polymerizable compound or the like is too small, the number of molecules bonded between fillers is too small, so that the strength is low. If it is too large, the glass transition temperature and the like are strongly exhibited, and the properties of the resin are strongly expressed. Therefore, it is desirable to appropriately adjust the surface modification amount according to the required characteristics.

[Inorganic filler] Examples of the first inorganic filler and the second inorganic filler include nitrides, carbides, carbon materials, metal oxides, and silicate minerals. The first inorganic filler and the second inorganic filler may be the same or different. Specifically, examples of the first inorganic filler and the second inorganic filler include boron nitride, boron carbide, boron carbonitride, graphite, carbon fiber, and carbon nanotubes as having high thermal conductivity and a very low or negative thermal expansion coefficient. Inorganic filler. Alternatively, alumina, silicon dioxide, magnesium oxide, zinc oxide, iron oxide, ferrite, mullite, cordierite, silicon nitride, and silicon carbide can be listed. Alternatively, an inorganic filler having a high thermal conductivity and a positive thermal expansion coefficient described below may be used for either the first inorganic filler or the second inorganic filler.

The third inorganic filler is preferably an inorganic filler having a high thermal conductivity or a smaller size than the first inorganic filler and the second inorganic filler, and having a thermal expansion coefficient different from that of the first inorganic filler and the second inorganic filler. Examples include: alumina, silicon dioxide, boron nitride, boron carbide, silicon carbide, aluminum nitride, silicon nitride, diamond, carbon nanotubes, graphite, graphene, silicon, berylia, and oxidation Magnesium, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide, cerium oxide, yttrium oxide, tin oxide, oxide's, bismuth oxide, cobalt oxide, calcium oxide, magnesium hydroxide, aluminum hydroxide, gold, silver, Copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, stainless and other inorganic filling materials and metal filling materials. The third inorganic filler may be unmodified, modified with a coupling agent, or modified with a coupling agent and a polymerizable compound.

The structure of the polymerizable compound desirably has a shape and a length capable of directly and efficiently 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 obtained heat radiation member requires insulation, as long as the desired insulation can be maintained, it may be an inorganic filler having conductivity. Examples of the shape of the inorganic filler include a plate shape, a spherical shape, an amorphous shape, a fibrous shape, a rod shape, and a cylindrical shape.

The inorganic filler is preferably boron nitride, aluminum nitride, silicon nitride, silicon carbide, graphite, carbon fiber, or carbon nanotube. Particularly 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, the dielectric constant of boron nitride is also low, and the insulation is also high. For example, if plate-shaped 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 materials during molding and hardening.

The average particle diameter of the inorganic filler is preferably from 0.1 μm to 200 μm. More preferably, it is 1 to 100 μm. When it is 0.1 μm or more, the thermal conductivity is good, and when it is 200 μm or less, the filling rate can be 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 particle diameter 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 diameter. The ratio of the inorganic filler to the coupling agent and the polymerizable compound depends on the amount of the coupling agent bonded to the inorganic filler used. As described above, the compound (for example, boron nitride) used as the first inorganic filler and the second inorganic filler has no reactive group on the surface and a reactive group exists only on the side surface. It is preferable that as many coupling agents as possible be bonded to the few reactive groups, so that organic compounds having the same or slightly more reactive groups are bonded. The reaction amount of the coupling agent to the inorganic filler mainly changes depending on the size of the inorganic filler or the reactivity of the coupling agent used. For example, the larger the inorganic filler, the smaller the area ratio of the side surface of the inorganic filler, and therefore the smaller the modification amount. Although it is intended to react as many coupling agents as possible, if the particles are reduced, the thermal conductivity of the product will be low, and therefore it is preferable to achieve equilibrium. The volume ratio of the coupling agent, the polymerizable compound, and the inorganic component in the exothermic member is preferably in a range of 5:95 to 30:70, and more preferably 10:90 to 25:75. The inorganic component refers to an inorganic raw material before being subjected to a silane coupling agent treatment or the like.

[Coupling Agent] The coupling agent bonded to the inorganic filler has a functional group capable of bonding to a functional group of a difunctional or more polymerizable compound. Examples of the coupling agent include a silane coupling agent represented by the following formula (3-1). (R ¹ -O) _j -Si (R ⁵ ) _3-j- (R ² ) _k- (R ³ ) _k- (R ⁴ ) _k -Ry (3-1) In the formula (3-1), , R ¹ is H-, or CH _3- (CH ₂ ) _{0 to 4-} ; R ² is-(CH ₂ ) _{0 to 3} -O-; R ³ is 1,3-phenylene, 1,4- Phenylene, naphthalene-2,6-diyl, or naphthalene-2,7-diyl; R ⁴ is-(NH) _{0 to 1-} (CH ₂ ) _{0 to 3-} ; R ⁵ is H-, or CH _3- (CH ₂ ) _{0 to 7-} ; Ry is oxetanyl, oxetanyl, amino, vinyl, carboxylic anhydride residue, or any polymerizable group containing these structures; j Is an integer of 0 to 3; k is an integer of 0 to 1; Formula (3-1) includes at least one of R ³ and R ⁴ .

When the functional group possessed by the difunctional or more polymerizable compound is an oxetanyl group or an acid anhydride residue, it is preferred to react with these functional groups, and therefore it is preferable to have an amine-based reactive group at the terminal. For example, Sila-Ace (registered trademark) S310, Sila-Ace S320, Sila-Ace S330 manufactured by JNC (stock), Sila-Ace S360, KBM903 and KBE903 manufactured by Shin-Etsu Chemical Industry Co., Ltd. When the terminal of the difunctional or more polymerizable compound is an amine, a coupling agent such as an oxetanyl group at the terminal is preferred. For example, Sila-Ace (registered trademark) S510, Sila-Ace S530 manufactured by JNC Corporation, etc. can be cited. Examples of the combination of the functional groups that form a bond between the coupling agent and the polymerizable compound include oxepropyl groups and amine groups, vinyl groups, methacryloxy groups, carboxyl or carboxylic anhydride residues, amines, and imidazoles. It is combined with oxetanyl and the like, but is not limited to these. What is necessary is just the combination of the functional group which can form the bond of a coupling agent and a polymerizable compound. More preferred is a combination with high heat resistance. The more the inorganic filler using a coupling agent is modified, the more the bond is increased, and therefore, it is preferable. The first coupling agent and the second coupling agent may be the same or different.

[Other components] The composition for an exothermic member may further include an organic compound (such as 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, A polymerization initiator or a solvent may be included.

[Unbonded polymerizable compound] The composition for an exothermic member may be a polymerizable compound (in this case, it may not necessarily be difunctional or more) that is not bonded by the inorganic filler as a constituent element. Such a polymerizable compound is preferably a compound that does not prevent thermal curing of the inorganic filler and does not evaporate or bleed out by heating. This 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 crystallinity 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 an exothermic member that does not contain an unbonded polymerizable compound, and measure the porosity to add a polymerizable compound in an amount to fill the void.

[Unbonded polymer compound] The composition for an exothermic member may include 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 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, examples thereof include: : Polyolefin resin, polyethylene resin, silicone resin, wax, etc. Regarding the content, it is desirable to first prepare a composition for an exothermic member that does not contain an unbonded polymer compound, and measure the porosity thereof to add a polymer compound in an amount that fills the void.

[Non-polymerizable liquid crystal compound] The composition for an exothermic member may include a liquid crystal compound having no polymerizable group as a constituent element. Examples of such non-polymerizable liquid crystal compounds are liquid crystals (LiqCryst, LCI Publisher GmbH, Hamburg, Germany) and the like as a date base of liquid crystal compounds. Be documented. By polymerizing the composition containing a non-polymerizable liquid crystal compound, for example, a composite material of a polymer of the compound (1-2) and a liquid crystal compound can be obtained. In such a composite material, a non-polymerizable liquid crystal compound exists in a polymer network such as a polymer dispersed liquid crystal. Accordingly, a liquid crystal compound having characteristics such as no fluidity in a temperature region to be used is desirable. After the inorganic filler is hardened, it is compounded by injecting voids in a temperature region showing an isotropic phase, and a liquid crystal compound of a component calculated in advance to fill the voids may be mixed with the inorganic filler. , Thereby polymerizing the inorganic fillers with each other.

[Polymerization initiator] The composition for an exothermic 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 diisobutyrate, lauryl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), and the like.

[Solvent] The composition for an exothermic member may contain a solvent. When the composition which needs to be polymerized is 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-processed 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.

[Others] In order to facilitate handling, a stabilizer may be added to the composition for an exothermic member. Such a stabilizer can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-third-butyl-4-hydroxytoluene (BHT). Furthermore, additives (oxides, etc.) may be added in order to adjust the viscosity or color of the composition for a heat radiation member. Examples include fine powders of titanium oxide to form white, carbon black to form black, and silicon dioxide to adjust viscosity. In addition, additives may be added in order to further increase the mechanical strength. Examples include inorganic fibers such as glass fibers, carbon fibers, and carbon nanotubes, or cloth, or fibers such as polyvinyl formaldehyde, polyvinyl butyral, polyester, polyamide, and polyimide as polymer additives. Or long molecules.

[Manufacturing Method] Hereinafter, a method for manufacturing a composition for a heat radiation member and a method for manufacturing a heat radiation member from the composition will be specifically described. (1) Coupling treatment is performed on the first inorganic filler, and one end of the coupling agent is bonded to the first inorganic filler. For the coupling treatment, a known method can be used. As an example, first, an inorganic filler and a coupling agent are added to a solvent. Stir with a stirrer or the like and dry. After the solvent is dried, a vacuum dryer is used to perform heat treatment under vacuum conditions. 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, the solvent was added to perform the same operation multiple times. The purified inorganic filler subjected to the coupling treatment was dried using an oven. (2) Modification with a polymerizable compound: A second inorganic filler is subjected to a coupling treatment (or the first inorganic filler subjected to the coupling treatment may be used as a 2 inorganic filler), and the difunctional polymerizable compound or more The other end of the coupling agent is bonded. As an example, the coupling-treated inorganic filler is mixed with a difunctional or more polymerizable compound 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) Mixing For example, the first inorganic filler and the second inorganic filler are weighed so that only the weight of the inorganic filler becomes 1: 1, and mixed with an agate mortar or the like. Thereafter, they are mixed using a double roll or the like to obtain a composition for a heat radiation member. Regarding the mixing ratio of the first inorganic filler and the second inorganic filler, 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 is, for example, The weight ratio is preferably 1: 1 to 1:30, and more preferably 1: 3 to 1:20. 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 secondary amine, it can react with two oxetanyl groups. The heterocyclopropyl side may be a small amount compared with the possibility of ring opening of the oxecyclopropyl side, and therefore it is preferably used by increasing the amount calculated based on the epoxy equivalent. (4) Production of a heat radiation member As an example, a method of manufacturing a film as a heat radiation member using a composition for a heat radiation member will be described. The composition for a heat radiation member was sandwiched in a hot plate using a compression molding machine, and orientation and hardening molding were performed by compression molding. Further, post-curing is performed using an oven or the like to obtain an exothermic member. The pressure during compression molding is preferably 50 kgf / cm ² to 200 kgf / cm ² , and more preferably 70 kgf / cm ² to 180 kgf / cm ² . The pressure during hardening is preferably high. However, it is preferable to appropriately change according to the fluidity of the mold or the target physical properties (in which direction the thermal conductivity is important, etc.), and to apply an appropriate pressure.

Hereinafter, the method of manufacturing the film as a heat radiation member using the composition for heat radiation members containing a solvent is demonstrated concretely. First, the composition is applied on a substrate and the solvent is dried and removed to form a coating film layer having a uniform film thickness. Examples of the coating method include spin coating, roll coat, curtain coat, flow coat, print, microgravure coat, and gravure coating. (Gravure coat), wire bar coat, dip coat, spray coat, meniscus coat method, and the like. The drying and removal of the solvent can be performed, for example, by air-drying at room temperature, drying by a hot plate, drying by a drying furnace, or blowing by warm air or hot air. The conditions for removing the solvent are not particularly limited, as long as it is dried until the solvent is substantially removed, and the fluidity of the coating film layer disappears.

Examples of the substrate include metal substrates such as copper, aluminum, and iron; inorganic semiconductor substrates such as silicon, silicon nitride, gallium nitride, and zinc oxide; alkali glass, borosilicate glass, and flint glass ( flint glass) and other glass substrates, alumina, aluminum nitride, and other inorganic insulating substrates; polyimide, polyimide, imine, polyimide, polyetherimide, polyetheretherketone, polyetherketone, polyimide Keto sulfide, polyether fluorene, polyfluorene, polyphenylene sulfide, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, Polycarbonate, Polyarylate, Acrylic Resin, Polyvinyl Alcohol, Polypropylene, Cellulose, Triethylpyrene Cellulose or Partial Saponified, Epoxy Resin, Phenolic Resin, Norbornene Resin and Other Plastic Films Substrate, etc.

The film substrate may be a uniaxially stretched film or a biaxially stretched film. The film substrate may be previously subjected to a surface treatment such as a saponification treatment, a corona treatment, or a plasma treatment. Furthermore, a protective layer which is not corroded by the solvent contained in the composition for a heat radiation member may be formed on these film substrates. Examples of the material used as the protective layer include polyvinyl alcohol. Furthermore, an anchor coat layer may be formed to improve the adhesion between the protective layer and the substrate. Such a tackifier coating may be any of an inorganic type and an organic type as long as it improves the adhesion between the protective layer and the substrate.

Hereinabove, the case where the bonds between the inorganic fillers are constituted by the inorganic fillers subjected to the coupling treatment and the inorganic fillers subjected to the coupling treatment and further modified with a polymerizable compound has been described. In addition, it is important in the present invention to realize the above-mentioned bonds between the inorganic fillers, and the coupling agent and the polymerizable compound may be bonded in advance using an organic synthesis technique, and then the coupling agent and the second inorganic filler may be used. Bonding. For example, the first inorganic filler is subjected to a coupling treatment with a silane coupling agent having an amine group. Next, a silane coupling agent having a vinyl group is modified with a polymerizable compound having a vinyl group and an epoxy group at each terminal, and then the second inorganic filler is coupled with the silane coupling agent. Finally, the amine group on the first inorganic filler side and the epoxy group on the polymerizable compound on the second inorganic filler side are bonded. Alternatively, only an inorganic filler modified by a coupling compound and then modified with a polymerizable compound may be used, and the polymerizable compounds may be bonded to each other with an appropriate polymerization initiator or the like to form a bond between the inorganic fillers.

The more the compound (1-2) has a large number of rings, the harder it is to soften at a higher temperature, and therefore, it is preferable as an exothermic material. As described above, if the polymerizable compound is polycyclic, heat resistance is increased, and if linearity is high, heat-induced extension or fluctuation between the inorganic fillers is small, and phonon conduction of heat can be efficiently transmitted. good. If it is polycyclic and has high linearity, as a result, liquid crystallinity is often exhibited. Therefore, if it is liquid crystallinity, it can be said that the thermal conductivity is improved. However, it was found that when a difunctional or more functional polymerizable compound represented by the formula (1-1) is used as the difunctional or more functional polymerizable compound, high thermal conductivity and high heat resistance can also be obtained. Compared with compound (1-2), compound (1-1) has a shorter molecular chain, is easier to synthesize, and is easier to handle, so it is preferred.

[Exothermic member] The exothermic member according to the second embodiment of the present invention is a cured product obtained by molding and curing the composition for an exothermic member according to the first embodiment according to the application. This hardened material has high thermal conductivity and high heat resistance, and has a negative or very small thermal expansion coefficient, and is excellent in chemical stability, hardness, and mechanical strength. In addition, the mechanical strength refers to Young's modulus, tensile strength, tear strength, flexural strength, flexural modulus of elasticity, impact strength, and the like. The heat radiation member of the present invention is useful 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.

As a condition for curing the composition for an exothermic member by thermal polymerization, the thermal curing temperature is from room temperature to 350 ° C, preferably from room temperature to 250 ° C, more preferably from 50 ° C to 200 ° C, and the curing time is 5 It is in the range of seconds to 10 hours, preferably 1 minute to 5 hours, and more preferably 5 minutes to 1 hour. After the polymerization, 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.

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

[Electronic device] An electronic device according to a third embodiment of the present invention includes the heat-radiating member according to the second embodiment, and an electronic device having a heat generating portion. The heat radiation member is disposed on the electronic device so as to be in contact with the heat generating portion. The shape of the heat release member may be any of a heat release electronic substrate, a heat release plate, a heat release sheet, a heat release film, a heat release adhesive, a heat release molded product, and the like. Examples of the electronic device include a semiconductor device. The exothermic member of the present application has high heat resistance and high insulation in addition to high thermal conductivity. Therefore, semiconductor devices are particularly effective for insulated gate bipolar transistors (IGBTs) that require a more efficient heat dissipation mechanism due to high power. IGBT is one of the semiconductor components. It is a bipolar transistor formed by combining a metal-Oxide-Semiconductor Field-Effect Transistor (MOSFET) into the gate, which can be used for power control applications. Examples of electronic devices equipped with IGBT include main converter elements of high-power inverters, non-stop power supply devices, variable voltage and frequency control devices for AC motors, control devices for railway vehicles, hybrid vehicles, and electric vehicles (electric car) and other electric conveyors, induction heat (IH) conditioners, etc.

As described above, in the compounding of an inorganic material and an organic compound, the present invention uses organic compounds to form a bond between the inorganic materials, thereby significantly improving thermal conductivity and heat resistance, and further controlling the thermal expansion rate. It should be noted that the functional group is an example, and is not limited to the functional group as long as the effect of the present invention can be obtained. [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 constituting the heat radiation member used in the examples of the present invention are as follows. <Inorganic Filler> · Boron nitride: h-BN particles, manufactured by Momentive Performance Materials Japan, (trade name) PolarTherm PTX-25 · boron nitride: h- BN particles, manufactured by Denka Corporation (trade name), (brand name) SGP • Alumina: Denka Corporation (trade name), DAW-20

<Silane coupling agent> · N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by JNC Corporation (trade name), S320 [Chem. 26] · 3-Aminopropyltriethoxysilane, manufactured by JNC (stock), (brand name) S330 [Chem. 27] · 3-Aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd. (trade name) KBM-903 [Chemical 28] · P-Aminophenyltrimethoxysilane, manufactured by GELEST, (brand name) SIA0599.1-d [Chem. 29]

<Polymerizable Compound> • Manufactured by Mitsubishi Chemical Corporation (trade name) jER YL6121H The following formula (1-11) and formula (1-12) are mixed 1: 1. [Chemical 30] (1-11) (1-12) · Mitsubishi Chemical Corporation (trade name) jER YX4000H [Chem. 31] -Made by JNC Corporation, the following formula (1-13) The following formula (1-13) can be synthesized by the method described in Japanese Patent No. 5084148. [Chemical 32] (1-13)

<Definition> In the following examples, the first inorganic filler bonded to the first coupling agent is referred to as filler A (boron nitride + silane coupling agent). A second inorganic filler that is a second inorganic filler bonded to a second coupling agent and further has a bifunctional or more functional polymerizable compound is referred to as filler B (boron nitride + silane coupling agent + polymerizable compound). The filler A and the filler B are bonded to each other as an exothermic member. FIG. 3 shows the manufacturing steps of the filler A, the filler B, and the heat radiation member.

〈Example 1〉 Filler A production step: 15 g of boron nitride particles (PolarTherm PTX-25 manufactured by Momentive Performance Materials Japan Co., Ltd.) and a silane coupling agent (Jie 2.25 g of S320 manufactured by JNC Corporation was added to 100 mL of toluene, and stirred at 500 rpm for 1 hour using a stirrer, and the obtained 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. Let the obtained particles be filler A.

· Filler B production steps: Measure 2 g of filler A particles and 3.2 g of polymerizable compound (jER YL6121H manufactured by Mitsubishi Chemical Corporation) using a double roll (IMC-AE00 type manufactured by Imoto Manufacturing Co., Ltd.) These were mixed at 120 ° C for 10 minutes. The weight ratio is the number of epoxy rings in which the amine groups in the filler A particles fully react, and the amount of the two rings being fully fused on the two rolls. The obtained mixture was added to 45 mL of tetrahydrofuran, and after sufficiently stirring, the insoluble component was settled by using a centrifugal separator (CR22N type high-speed cooling centrifuge manufactured by Hitachi Koki Co., Ltd., 4,000 revolutions × 10 minutes × 25 ° C). The solution containing the components in which the unreacted polymerizable compound was dissolved was removed by decantation. Then, 45 mL of acetone was added, and the same operation as described above was performed. Furthermore, the same operation was repeated in the order of tetrahydrofuran and acetone. The insoluble component was dried, and the obtained particles were set as filler B.

· Exothermic member production steps: Weigh 0.46 g of filler A and 0.24 g of filler B, mix them, sandwich them in a stainless steel plate, and use a compression molding machine set at 150 ° C (IMC-19EC manufactured by Imoto Manufacturing Co., Ltd.). Press to 30 MPa and heat for 15 minutes to perform alignment treatment and pre-hardening. That is, when the mixture is expanded between the stainless steel plates, since the BN particles are plate-like particles, the particles are aligned parallel to the stainless steel plate. The amount of the sample was adjusted so that the thickness of the sample was about 300 μm. Furthermore, it hardened | cured at 120 degreeC using the oven for 12 hours. The sample obtained in this operation was set as an exothermic member.

<Evaluation> • Thermogravimetric (TG) measurement of the amount of coating of inorganic fillers by fillers A, B, and exothermic members, polymerizable compounds, or silane coupling agents. Thermogravimetric and differential thermal measurement devices (Rigaku) TG-8121 (manufactured) was calculated from the heating loss at 910 ° C. The 5% weight reduction temperature of the exothermic member was calculated from the temperature at the time of 5% weight reduction when the reduction amount of 140 ° C to 900 ° C was set to 100% by weight using the measurement device. · Evaluation of thermal expansion coefficient A test piece of 3 mm × 15 mm was cut out from the obtained sample, and the thermal expansion coefficient was determined in a range of 50 ° C to 200 ° C. The thermal expansion coefficient was measured using a TMA-SS6100 thermomechanical analysis device manufactured by SII. Evaluation of color A 15 mm × 15 mm test piece was cut out of the obtained sample, and the color was measured. Color was measured using a spectrophotometer SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.

<Example 2> In Example 2, the double-roll heating temperature of the filler B step was set to 150 ° C.

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

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

<Example 13> As the silane coupling agent of Example 13, SIA0599.1-d (p-aminophenyltrimethoxysilane) manufactured by GELEST was used. Filler A production step: 7 g of boron nitride particles (SGP manufactured by Denka Corporation) and 0.36 g of silane coupling agent (SIA0599.1-d) are added to 20 mL of methanol and 50 mL of water. The mixture was stirred at 920 rpm at 60 ° C. for 1 hour using a stirrer, and the obtained mixture was allowed to stand overnight. Furthermore, after drying the solvent, a vacuum dryer set at 120 ° C. was used to perform heat treatment under vacuum for 5 hours. Let the obtained particles be filler A. · Filler B production step Measure 2.56 g of filler A particles and 4.8 g of polymerizable compound (jER YX4000H manufactured by Mitsubishi Chemical Corporation), using a double roll (IMC-AE00 type manufactured by Imoto Manufacturing Co., Ltd.) These were mixed at 180 ° C for 10 minutes. The weight ratio is the number of epoxy rings in which the amine groups in the filler A particles fully react, and the amount of the two rings being fully fused on the two rolls. The obtained mixture was added to 45 mL of tetrahydrofuran, and after sufficiently stirring, the insoluble component was settled by using a centrifugal separator (CR22N type high-speed cooling centrifuge manufactured by Hitachi Koki Co., Ltd., 4,000 revolutions × 10 minutes × 25 ° C). The solution containing the components in which the unreacted polymerizable compound was dissolved was removed by decantation. Then, 45 mL of acetone was added, and the same operation as described above was performed. Furthermore, the same operation was repeated in the order of tetrahydrofuran and acetone. The insoluble component was dried, and the obtained particles were set as filler B.

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

<Comparative Example 1, Comparative Example 2> In Comparative Examples 1 and 2, SGP manufactured by Denka Corporation was used as the BN particles. As the silane coupling agent of Comparative Example 1, KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd. was used. As the silane coupling agent of Comparative Example 2, S320 manufactured by JNC Corporation was used. As the crosslinkable polymerizable compound, Formula (1-13) manufactured by JNC Corporation was used.

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

[Table 1] Table 1: Preparation steps of filler A

[Table 2] Table 2: Preparation steps of filler B

[Table 3] Table 3: Manufacturing steps of exothermic components

[Table 4] Table 4: Weight reduction temperature, thermal expansion rate, color

The 5% weight reduction temperature of Examples 1 to 16 is higher than that of Comparative Examples 1 to 3. The organic components (polymerizable compounds and silane coupling agents) of the examples have few substituents and are not easily affected by heat. Therefore, it is considered that the heat resistance of the exothermic member is improved. Furthermore, in cases where the thermal expansion coefficients of Examples 1 to 16 are positive and negative, the thermal expansion of the heat releasing member can be controlled by combination. Furthermore, L * of Examples 1 to 16 increased the brightness as compared with Comparative Examples 1 to 3. The reason is considered to be that compared with the comparative example, the organic component of the example has fewer substituents, suppresses coloring by oxidation, and increases the white tone. The polymerizable compound used in Examples 1 to 16 has a shorter molecular chain than the polymerizable compound exhibiting liquid crystallinity, but the heat releasing members of Examples 1 to 16 can have high thermal conductivity and high heat resistance.

Regarding the publications cited in this specification, and all documents including Japanese patent applications and Japanese patents, each document is specifically indicated and referred to and incorporated into this specification, and the entire content of this document is described in this specification. The same degree is incorporated into this specification by reference.

The use of nouns and the same designations used in connection with the description of the present invention (especially in connection with the scope of patent applications below) can be understood as involving singular and plural as long as they are not specifically mentioned in this specification or are not clearly contradictory to context Both. The phrases "including", "having", "containing", and "including" can be understood as open end terms (ie, meaning of "including-but not limited to") unless otherwise specified. The detailed description of the numerical range in this specification is only intended to play a role as a notation to describe each value within the range as long as it is not specifically stated in the specification, such as listing each value in this specification one by one Generally incorporated into the manual. All the methods described in this specification can be performed in all appropriate order as long as they are not specifically pointed out in this specification or are not clearly contradictory to context. All examples or illustrative words (such as "etc.") used in this specification are only intended to better illustrate the present invention, and are not intended to limit the scope of the present invention, unless otherwise specifically claimed. Any wording in the specification should not be interpreted to mean an element that is not described in the scope of a patent application that is indispensable for implementing the present invention.

In this specification, in order to implement the present invention, a preferred embodiment of the present invention will be described including the best form known to the inventors. For those skilled in the art, after reading the description, modifications of these preferred embodiments will be apparent. The inventor anticipates that a skilled person may suitably apply such a modification, and plans to implement the present invention by methods other than those specifically described in this specification. Therefore, as permitted by the benchmark method, the present invention includes all changes and equivalents described in the scope of patent application accompanying this specification. Furthermore, as long as it is not specifically mentioned in this specification or contradictory to context, any combination of the said elements in all the modifications is included in this invention.

1‧‧‧ 1st inorganic filler, boron nitride

2‧‧‧ 2nd inorganic filler, boron nitride

11‧‧‧ the first coupling agent

12‧‧‧ 2nd coupling agent

22‧‧‧ polymerizable compound

FIG. 1 is a conceptual diagram showing the bond between inorganic fillers using a boron nitride as an example in the exothermic member of the present application. FIG. 2 is a conceptual diagram showing that the other end of the coupling agent 11 bonded to the first inorganic filler 1 and the polymerizable compound 22 of the second inorganic filler 2 are bonded by curing of the composition for an exothermic member. FIG. 3 is a conceptual diagram showing the manufacturing steps of the filler A, the filler B, and the heat radiation member.

Claims (8)

A composition for an exothermic member, comprising: a thermally conductive first inorganic filler bonded to one end of a first coupling agent; and a thermally conductive second inorganic filler bonded to one end of a second coupling agent, wherein The other end of the second coupling agent is further bonded to a second inorganic filler having a difunctional polymerizable compound or more, and the second coupling agent is bonded to a polymerizable compound represented by the following formula (1-1). As the difunctional or more functional polymerizable compound, the polymerizable compound is a non-liquid crystalline compound, and at least one of the functional groups of the polymerizable compound can be bonded to the other end of the first coupling agent, R ^a -R ⁶ -O- (Rx) _n -OR ¹¹ -R ^a (1-1) In the formula (1-1), R ^a is the following formula (2-1) to formula (2- 2), an amine group, a vinyl group, a carboxylic acid anhydride residue, or any polymerizable group containing these structures; Rx is any one of the following formulae (2-3) to (2-6); n is An integer of 1 to 3; R ⁶ and R ¹¹ are each independently a single bond or an alkylene group having 1 to 20 carbon atoms, 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 (2-4) to (2-6), R ⁷ to R ¹⁰ are each independently hydrogen or an alkylene group having 1 to 20 carbon atoms. The composition for an exothermic member according to item 1 of the scope of patent application, wherein the first inorganic filler and the second inorganic filler are bonded with a silane coupling agent represented by the following formula (3-1) as the The first coupling agent and the second coupling agent, (R ¹ -O) _j -Si (R ⁵ ) _3-j- (R ² ) _k- (R ³ ) _k- (R ⁴ ) _k -Ry (3 -1) In the formula (3-1), R ¹ is H-, or CH _3- (CH ₂ ) _{0 to 4-} ; R ² is-(CH ₂ ) _{0 to 3} -O-; R ³ is 1,3-phenylene, 1,4-phenylene, naphthalene-2,6-diyl, or naphthalene-2,7-diyl; R ⁴ is-(NH) _{0 to 1-} (CH ₂ ) _{0 to 3-} ; R ⁵ is H-, or CH _3- (CH ₂ ) _{0 to 7-} ; Ry is oxetanyl, oxetanyl, amino, vinyl, carboxylic anhydride residue, or Any polymerizable group containing these structures; j is an integer of 0 to 3; k is an integer of 0 to 1; Formula (3-1) includes at least one of R ³ and R ⁴ . The composition for an exothermic member according to item 1 or item 2 of the scope of the patent application, wherein the first inorganic filler and the second inorganic filler are selected from the group consisting of boron nitride, boron carbide, boron carbonitride, Graphite, carbon fiber, carbon nanotube, graphene, alumina, aluminum nitride, silicon dioxide, silicon nitride, silicon carbide, zinc oxide, magnesium oxide, magnesium hydroxide, cordierite, or iron oxide-based materials At least one. The composition for an exothermic member according to claim 1 or claim 2, further comprising a third inorganic filler having a thermal expansion coefficient different from that of the first inorganic filler and the second inorganic filler. The composition for an exothermic member according to claim 1 or claim 2, further comprising an organic compound or a polymer compound not bonded to the first inorganic filler and the second inorganic filler. A heat-radiating member is obtained by curing the composition for a heat-radiating member according to any one of claims 1 to 5 of the scope of patent application. An electronic device includes: the heat-radiating member according to item 6 of the scope of patent application; and an electronic device having a heat-generating portion, and the heat-radiating member is disposed on the electronic device in contact with the heat-generating portion. A method for producing a heat-radiating member, comprising: a step of bonding a thermally conductive first inorganic filler to one end of a first coupling agent; a step of bonding a thermally conductive second inorganic filler to one end of a second coupling agent; A step of bonding the other end of the second coupling agent to a difunctional or higher polymerizable compound; and a step of bonding the other end of the first coupling agent to the difunctional or higher polymerizable compound; and The difunctional or more polymerizable compound is a polymerizable compound represented by the following formula (1-1), the polymerizable compound is a non-liquid crystal compound, and R ^a -R ⁶ -O- (Rx) _n -OR ¹¹ -R ^a (1-1) In the formula (1-1), R ^a is the following formula (2-1) to formula (2-2), an amino group, a vinyl group, a carboxylic acid anhydride residue, Or any polymerizable group containing these structures; Rx is any one of the following formulae (2-3) to (2-6); n is an integer of 1 to 3; R ⁶ and R ¹¹ are each independently Is a single bond or an alkylene group having 1 to 20 carbon atoms, 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 (2-4) to (2-6), R ⁷ to R ¹⁰ are each independently hydrogen or an alkylene group having 1 to 20 carbon atoms.