Curable composition, thermally conductive material, thermally conductive sheet, and device with thermally conductive layer

Abstract

The present invention addresses the problem of providing: a curable composition from which it is possible to form a thermally conductive material having excellent thermal conductivity; a thermally conductive material; a thermally conductive sheet; and a device provided with a thermally conductive layer. The curable composition according to the present invention contains a phenolic compound, an epoxy compound, an aggregated boron nitride, and an inorganic substance X. The inorganic substance X is at least one selected from the group consisting of aluminum oxide and silicon dioxide. The average particle diameter of the aggregated boron nitride is 20 μm or more. The average particle diameter of the inorganic substance X is 0.30 μm or less.

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a thermally conductive material, a thermally conductive sheet, and a device with a thermally conductive layer. [Background technology]

[0002] Power semiconductor devices used in electrical equipment such as personal computers, general home appliances, and automobiles have been rapidly becoming smaller in size in recent years. As the devices become smaller, their density increases, and controlling the heat generated by these devices becomes an issue. To address the above problems, thermally conductive materials are used to facilitate heat dissipation from power semiconductor devices. For example, Patent Document 1 discloses a thermally conductive composition containing boron nitride and the like. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-177562 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have studied compositions such as those described in Patent Document 1 and have found that there is room for improvement in the thermal conductivity of the resulting thermally conductive material.

[0005] Therefore, an object of the present invention is to provide a curable composition that can form a thermally conductive material having excellent thermal conductivity. Another object of the present invention is to provide a thermally conductive material, a thermally conductive sheet, and a device with a thermally conductive layer, which are related to the curable composition. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] A composition comprising a phenolic compound, an epoxy compound, aggregated boron nitride, and inorganic substance X; The inorganic substance X is at least one selected from the group consisting of aluminum oxide and silicon dioxide, The average particle size of the aggregated boron nitride is 20 μm or more, The curable composition, wherein the inorganic substance X has an average particle size of 0.30 μm or less. [2] The curable composition according to [1], wherein the inorganic substance X has an average particle size of 0.25 μm or less. [3] The curable composition according to [1] or [2], wherein the mass ratio of the content of the aggregated boron nitride to the content of the inorganic substance X is 5.0 to 25.0. [4] Further, a surface modifier is contained, The curable composition according to any one of [1] to [3], wherein the aggregated boron nitride, together with the surface modifier adsorbed onto the surface of the aggregated boron nitride, constitutes surface-modified aggregated boron nitride. [5] The curable composition according to any one of [1] to [4], which satisfies at least one of the following requirements: the phenol compound contains a phenol compound having a triazine skeleton; and the epoxy compound contains an epoxy compound having a triazine skeleton. [6] The curable composition according to any one of [1] to [5], further comprising a curing accelerator. [7] The curable composition according to [6], wherein the curing accelerator includes a compound having a phosphorus atom. [8] The curable composition according to any one of [1] to [7], further comprising an ion scavenger. [9] The curable composition according to any one of [1] to [8], further comprising a maleimide compound.

[10] A thermally conductive material obtained by curing the curable composition according to any one of [1] to [9].

[11] A thermally conductive sheet made of the thermally conductive material according to

[10] .

[12] A device with a thermally conductive layer, comprising: a device; and a thermally conductive layer disposed on the device, the thermally conductive layer comprising the thermally conductive material according to

[10] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a curable composition that can form a thermally conductive material having excellent thermal conductivity. Furthermore, according to the present invention, it is possible to provide a thermally conductive material, a thermally conductive sheet, and a device with a thermally conductive layer, which are related to the curable composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] The curable composition, the thermally conductive material, the thermally conductive sheet, and the device with a thermally conductive layer of the present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0010] In this specification, the term "(meth)acryloyl group" means "either one or both of an acryloyl group and a methacryloyl group." The term "(meth)acrylamide group" means "either one or both of an acrylamide group and a methacrylamide group." The term "(meth)acryl" means "either one or both of acryl and methacryl."

[0011] In this specification, the acid anhydride group may be a monovalent group or a divalent group. When the acid anhydride group represents a monovalent group, examples thereof include substituents obtained by removing any hydrogen atom from acid anhydrides such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. When the acid anhydride group represents a divalent group, it is intended to mean a group represented by *-CO-O-CO-*, where * represents a bonding position. In this specification, the bonding direction of a divalent group (e.g., -COO-) is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ," the compound may be "XO-CO-Z" or "X-CO-OZ."

[0012] In this specification, a substituent or the like that is not specified as substituted or unsubstituted may, if possible, further have a substituent (for example, a group exemplified by the substituent group Y described later) within a range that does not impair the intended effect. For example, the expression "alkyl group" means a substituted or unsubstituted alkyl group (an alkyl group that may have a substituent) within a range that does not impair the intended effect. In the present specification, when it is stated that a compound may have a substituent, the type, position, and number of the substituents are not particularly limited. The number of the substituents may be, for example, one or two or more. The substituents may be, for example, monovalent nonmetallic atomic groups excluding hydrogen atoms, and are preferably groups selected from the substituent group Y. In this specification, examples of halogen atoms include chlorine atoms, fluorine atoms, bromine atoms, and iodine atoms.

[0013] (Substituent group Y) Halogen atoms (such as -F, -Br, -Cl, and -I), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate base groups, carboxylic anhydride groups, cyanate ester groups, unsaturated polymerizable groups, epoxy groups, oxetanyl groups, aziridinyl groups, thiol groups, isocyanate groups, thioisocyanate groups, aldehyde groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, N-alkylamino groups, N,N-dialkylamino groups, N-arylamino groups, N,N-diarylamino groups, and N-alkyl-N-arylamino groups , an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N,N-dialkylcarbamoyloxy group, an N,N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, an acylthio group, an acylamino group, an N-alkylacylamino group, an N-arylacylamino group, a ureido group, an N'-alkylureido group, an N',N'-dialkylureido group, an N'-arylureido group, an N',N'-diarylureido group, N'-Alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N',N'-dialkyl-N-alkylureido group, N',N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N',N'-diaryl-N-alkylureido group, N',N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group , N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO3H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N,N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N,N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (-SONHSO(alkyl)) and its conjugate base group, N-arylsulfonylsulfamoyl group (-SONHSO(aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (-CONHSO(alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (-CONHSO(aryl)) and its conjugate base group, alkoxysilyl group (-Si(Oalkyl)3), aryloxysilyl group (-Si(Oaryl)3), hydroxysilyl group (-Si(OH)3) and its conjugate base group, phosphono group (-PO3H2) and its conjugate base group, dialkylphosphono group (-PO3(alkyl) )2), diarylphosphono group (-PO3(aryl)2), alkylarylphosphono group (-PO3(alkyl)(aryl)), monoalkylphosphono group (-PO3H(alkyl)) and its conjugate base group, monoarylphosphono group (-PO3H(aryl)) and its conjugate base group, phosphonooxy group (-OPO3H2) and its conjugate base group, dialkylphosphonooxy group (-OPO3(alkyl)2), diarylphosphonooxy group (-OPO3(aryl)2), alkylarylphosphonooxy group (-OPO3(alkyl)(aryl)), monoalkylphosphonooxy group (-OPO3H(alkyl)) and its conjugate base group, monoarylphosphonooxy group (-OPO3H(aryl)) and its conjugate base group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group, and alkyl group. Furthermore, each of the above groups may have further substituents (e.g., one or more of the above groups) if possible. For example, an aryl group which may have a substituent is also included as a group which can be selected from the substituent group Y. When a group selected from the substituent group Y has a carbon atom, the group preferably has 1 to 20 carbon atoms. The number of atoms other than hydrogen atoms contained in the group selected from the substituent group Y is preferably 1 to 30. Furthermore, if possible, these substituents may bond with each other or with the group they substitute to form a ring, or they may not form a ring. For example, an alkyl group (or an alkyl group portion in a group containing an alkyl group as a partial structure, such as an alkoxy group) may be a cyclic alkyl group (cycloalkyl group) or an alkyl group having one or more cyclic structures as a partial structure.

[0014] [Composition] The curable composition of the present invention (hereinafter also simply referred to as "composition") contains a phenol compound, an epoxy compound, aggregated boron nitride, and inorganic substance X described below, wherein the aggregated boron nitride has an average particle size of 20 μm or more, and the inorganic substance X has an average particle size of 0.30 μm or less. Hereinafter, the aggregated boron nitride having an average particle size of 20 μm or more and the inorganic substance X having an average particle size of 0.30 μm or less will also be referred to simply as the specific inorganic substance.

[0015] The mechanism by which the above-described configuration solves the problems of the present invention is not clear, but the inventors speculate as follows. The inorganic substance X having a predetermined particle size has an average particle size smaller than that of the aggregated boron nitride having a predetermined particle size. In the thermally conductive material, such inorganic substance X can exist between the predetermined aggregated boron nitride particles. As a result, it is presumed that the thermally conductive material has excellent thermal conductivity due to the reduced voids between the specific inorganic substances. Hereinafter, the excellent thermal conductivity of a thermally conductive material formed using the composition is also referred to as the excellent effect of the present invention.

[0016] The components contained in the composition are described in detail below.

[0017] [Phenol compounds] The compositions of the present invention include a phenolic compound. A phenolic compound is a compound having one or more hydroxyl groups (for example, phenolic hydroxyl groups) directly bonded to an aromatic ring group. The number of hydroxyl groups directly bonded to the aromatic ring group of the phenol compound is preferably 2 or more, and more preferably 2 to 10. The phenol compound preferably has a triazine skeleton. Having a triazine skeleton means that the phenol compound has one or more (for example, 1 to 5) triazine ring groups in the compound.

[0018] (Compound represented by formula (Z)) The phenol compound is preferably a compound represented by formula (Z).

[0019] [ka]

[0020] In formula (Z), when there are multiple groups represented by the same symbol, the multiple groups represented by the same symbol may be the same or different, unless otherwise specified.

[0021] In formula (Z), E 1 ~E 6 each independently represents a single bond, —NH—, or —NR—. E 1 ~E 6 are each independently preferably -NH- or -NR-, and more preferably -NH-. R represents a substituent, and examples of the substituent represented by R include linear or branched alkyl groups having 1 to 5 carbon atoms.

[0022] In formula (Z), B 1 represents a single bond or a k+1 valent organic group. 2 represents a single bond or an (l+1)-valent organic group. 3 represents a single bond or an (m+1)-valent organic group. 4 represents a single bond or an (n+1)-valent organic group. The values ​​of k, l, m, and n in the k+1-valent organic group, the l+1-valent organic group, the m+1-valent organic group, and the n+1-valent organic group are the same as the values ​​of k, l, m, and n in formula (Z). In addition, if r is 2 or more and the values ​​of m are different, B 3The value of m in the (m+1) valent organic group represented by 3 X to which 3 The value of m is the same as the number of

[0023] B 1 ~B 4 Examples of the organic group represented by include groups in which j hydrogen atoms have been removed from a hydrocarbon having 1 to 20 carbon atoms and which may have a heteroatom. Here, j refers to k+1, l+1, m+1, or n+1. Here, examples of the hydrocarbon before removing j hydrogen atoms include one or more hydrocarbons selected from the group consisting of an aliphatic hydrocarbon having 1 to 20 carbon atoms which may have a substituent, an aliphatic ring having 3 to 20 carbon atoms which may have a substituent, and an aromatic ring having 3 to 20 carbon atoms which may have a substituent. In addition, the group obtained by removing j hydrogen atoms from the above hydrocarbon may further include -O-, -S-, -CO-, -NR N R may be a group formed by combining one or more divalent linking groups selected from the group consisting of - and -SO2-. N represents a hydrogen atom or a substituent. Examples of aliphatic hydrocarbons having 1 to 20 carbon atoms include methane, ethane, propane, butane, pentane, hexane, and heptane. Examples of the aliphatic ring having 3 to 20 carbon atoms include a cyclohexane ring, a cycloheptane ring, a norbornane ring, and an adamantane ring. Examples of aromatic rings having 3 to 20 carbon atoms include aromatic hydrocarbon rings having 6 to 20 carbon atoms and aromatic heterocyclic rings having 3 to 20 carbon atoms. Examples of the aromatic hydrocarbon ring having 6 to 20 carbon atoms include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of aromatic heterocycles having 3 to 20 carbon atoms include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a carbazole ring, an indole ring, and a benzothiazole ring.

[0024] In formula (Z), k, l, m, and n each independently represent an integer of 0 or greater, provided that the sum of k, l, r×m, and n is 2 or greater, and is preferably an integer of 2 to 12, and more preferably an integer of 4 to 8. The value of m in "r×m" is the average value of multiple possible m's. k, l, m and n each independently represent preferably 0 to 5, more preferably 1 or 2. Among these, it is preferable that k is 1 or more (for example, 1 to 2), l is 1 or more (for example, 1 to 2), m is 1 or more (for example, 1 to 2), and n is 1 or more (for example, 1 to 2). Note that if k is 0, B 1 is X 1 If l is 0, then B 2 is X 2 If m is 0, then B 3 is X 3 If n is 0, then B 4 is X 4 does not have. Also, B 1 When B is a single bond, k is 1. 2 When is a single bond, l is 1. 3 When B is a single bond, m is 1. 4 is a single bond, then n is 1.

[0025] L represents a divalent organic group. Examples of the divalent organic group include an aromatic ring group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, -O-, -S-, -N(R N )-, -CO-, and combinations thereof. N represents a hydrogen atom or a substituent. N Examples of the substituent represented by include a linear alkyl group and a branched alkyl group having 1 to 5 carbon atoms. Furthermore, examples of the substituent that the aromatic ring group, aliphatic hydrocarbon group, and aliphatic ring group represented by L may have include linear alkyl groups and branched alkyl groups having 1 to 5 carbon atoms.

[0026] Examples of the aromatic ring group include aromatic hydrocarbon ring groups having 6 to 20 carbon atoms and aromatic heterocyclic groups having 3 to 20 carbon atoms. Examples of aromatic hydrocarbon ring groups having 6 to 20 carbon atoms include groups in which two hydrogen atoms have been removed from an aromatic ring. Examples of the aromatic ring include monocyclic aromatic rings such as a benzene ring, and polycyclic aromatic rings such as a naphthalene ring and an anthracene ring. Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include groups in which two hydrogen atoms have been removed from an aromatic heterocycle. Examples of the aromatic heterocycle include monocyclic aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, and a thiazole ring, and polycyclic aromatic heterocycles such as a benzothiazole ring, a carbazole ring, and an indole ring.

[0027] Examples of the aliphatic hydrocarbon group include alkylene groups having 1 to 12 carbon atoms, and specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, methylhexylene, and heptylene groups.

[0028] Examples of the aliphatic ring group include groups in which two hydrogen atoms have been removed from an aliphatic ring. Examples of the aliphatic ring include a cyclohexane ring, a cycloheptane ring, a norbornane ring, and an adamantane ring.

[0029] An aromatic ring group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, or -O-, -S-, -NR N The group combining - or -CO- may be not only a divalent linking group formed by combining two or more of these, but also a divalent linking group formed by combining two or more of the same type of groups (for example, aromatic ring groups) via a single bond.

[0030] In order to obtain a thermally conductive material with superior thermal conductivity, it is preferable that both ends of L are carbon atoms. The terminal carbon atoms may be part of a cyclic structure. Furthermore, in order to obtain a thermally conductive material with better thermal conductivity, it is preferable that L in the above formula (Z) be a divalent organic group having at least one selected from the group consisting of an optionally substituted divalent aromatic ring group, an optionally substituted divalent aliphatic ring group, and an optionally branched alkylene group having two or more carbon atoms, and a divalent organic group having an optionally substituted divalent aromatic ring group is more preferable in terms of obtaining better thermal conductivity.

[0031] In formula (Z), r is an integer of 0 or more. r is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.

[0032] In formula (Z), X 1 ~X 4 each independently represents an aromatic ring group having a phenolic hydroxyl group. The "aromatic ring group having a phenolic hydroxyl group" may be an aromatic ring group having one or more (for example, 1 to 4) hydroxyl groups (phenolic hydroxyl groups) directly bonded to the aromatic ring. The aromatic ring group may or may not have a substituent other than the hydroxyl group. The aromatic ring group may be monocyclic or polycyclic and may have a heteroatom as a ring member atom. The number of ring members of the aromatic ring group is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6. The aromatic ring group is preferably a benzene ring group. The substituent that the aromatic ring group may have other than the hydroxyl group is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

[0033] In formula (Z), there are k X 1 , there are l X 2 , r×m pieces of X 3 and n X's 4It is also preferred that at least one of the groups is an aromatic ring group having a phenolic hydroxyl group and a substituent located at the ortho-position of the phenolic hydroxyl group. The substituent may be located at only one or both of the ortho-positions of the phenolic hydroxyl group. The value of m in "r×m" is the average value of multiple possible m's. Furthermore, the "substituent located at the ortho position" is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. In other words, there are (k+l+r×m+n) X 1 ~X 4 Among the "aromatic ring groups having a phenolic hydroxyl group" represented by any one of the above, at least one (preferably 30% or more, more preferably 50% or more, and even more preferably 65% ​​or more; preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less) may represent an "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho-position of the phenolic hydroxyl group".

[0034] X 1 ~X 4 In the aromatic ring group having a phenolic hydroxyl group represented by the formula (I), the aromatic ring group other than "an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho-position of the phenolic hydroxyl group" may or may not have a substituent other than a hydroxyl group (phenolic hydroxyl group). Examples of aromatic ring groups other than "aromatic ring groups having a phenolic hydroxyl group and a substituent positioned at the ortho-position of the phenolic hydroxyl group" include hydroxyphenyl groups. There are (k+l+r×m+n) instances of X 1 ~X 4 It is also preferred that at least one (e.g., 1 to 2) of the "aromatic ring group having a phenolic hydroxyl group" represented by any one of the above is an aromatic ring group other than the "aromatic ring group having a phenolic hydroxyl group and a substituent positioned at the ortho-position of the phenolic hydroxyl group". X 1 ~X 4In the aromatic ring group having a phenolic hydroxyl group represented by the formula (I), the presence of aromatic ring groups other than "an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho-position of the phenolic hydroxyl group" is thought to disrupt the symmetry of the compound as a whole, lower the melting point of the compound, and improve the handleability of a semi-cured film formed from the composition.

[0035] (Compound represented by formula (Z1)) The phenol compound is also preferably a compound represented by formula (Z1). The phenol compound preferably contains a compound represented by formula (Z1), and the phenol compound may be the compound represented by formula (Z1) itself. The content of the compound represented by formula (Z1) is preferably from 10 to 100 mass %, more preferably from 25 to 100 mass %, and even more preferably from 50 to 100 mass %, based on the total mass of the phenol compound.

[0036] [ka]

[0037] In formula (Z1), r represents an integer of 0 or greater. r is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10. L represents a divalent organic group. The divalent organic group represented by L in formula (Z1) is, for example, the same as the divalent organic group represented by L in formula (Z1). R Z represents a hydrogen atom or a substituent. R Z The substituent represented by the formula (I) is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. There are (3+r) Rs in formula (Z1) Z At least one of (preferably 30% or more, more preferably 50% or more, even more preferably 65% ​​or more; preferably 90% or less, more preferably 80% or less) may represent a substituent. There are (3+r) Rs in formula (Z1) Z At least one (for example, 1 to 2) of these may represent a hydrogen atom. R in formula (Z1) z (Preferably, the substituent R z ) and OH-bonded benzene ring group, z (Preferably, the substituent R z ) is also preferably present at the para position relative to the NH bonded to the benzene ring group.

[0038] (Compound represented by formula (Z2)) The phenol compound is also preferably a compound represented by formula (Z2). The phenol compound preferably contains a compound represented by formula (Z2), and the phenol compound may be the compound represented by formula (Z2) itself. The content of the compound represented by formula (Z2) is preferably 10 to 100 mass%, more preferably 25 to 100 mass%, and even more preferably 50 to 100 mass%, based on the total mass of the phenol compound.

[0039] [ka]

[0040] In formula (Z2), R Z represents a hydrogen atom or a substituent. Two Rs Z At least one of these groups preferably represents a substituent, and both of these groups preferably represent a substituent. R Z The substituent represented by the formula (I) is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched. It is also preferred that the alkyl group is unsubstituted. The two R in formula (Z2) z may be the same or different.

[0041] The phenol compound may contain other phenol compounds in addition to those mentioned above. Other phenol compounds include, for example, benzene polyols such as bisphenol A, F, S, AD, benzene diol, and benzene triol, biphenyl aralkyl phenol resins, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, polyhydric phenol novolac resins synthesized from polyhydric hydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylol methane resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol phenol co-condensed novolac resins, naphthol cresol co-condensed novolac resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and alkoxy group-containing aromatic ring-modified novolac resins.

[0042] The molecular weight of the phenol compound is preferably 225 to 2,000, more preferably 225 to 1,000. When the molecular weight has a molecular weight distribution, the molecular weight is a weight average molecular weight.

[0043] The hydroxyl group content of the phenol compound is preferably 2.0 mmol / g or more, more preferably 4.0 mmol / g or more, and the upper limit is preferably 25.0 mmol / g or less, more preferably 10.0 mmol / g or less. The hydroxyl group content refers to the number of hydroxyl groups (preferably phenolic hydroxyl groups) that 1 g of the phenol compound has. In addition to hydroxyl groups, the phenolic compound may or may not have active hydrogen-containing groups (such as carboxylic acid groups) capable of polymerizing with the epoxy compound. The lower limit of the active hydrogen content of the phenolic compound (the total content of hydrogen atoms in hydroxyl groups, carboxylic acid groups, etc.) is preferably 2.0 mmol / g or more, more preferably 4.0 mmol / g or more. The upper limit is preferably 25.0 mmol / g or less, more preferably 10.0 mmol / g or less.

[0044] The composition of the present invention may contain, in addition to the above phenolic compound, a compound having a group capable of reacting with an epoxy compound (hereinafter also referred to as "other active hydrogen-containing compounds"). The mass ratio of the content of the other active hydrogen-containing compound to the content of the phenol compound is preferably 0 to 1, more preferably 0 to 0.1, and even more preferably 0 to 0.05.

[0045] The phenol compounds may be used alone or in combination of two or more. The content of the phenol compound is preferably 3.0 to 90.0 mass %, more preferably 5.0 to 50.0 mass %, still more preferably 7.0 to 40.0 mass %, and particularly preferably 7.0 to 15.0 mass %, based on the total solid content of the composition. The above-mentioned solid content refers to the components that form the thermally conductive material and does not include solvents. Note that the components that form the thermally conductive material may be components that undergo a reaction (polymerization) and change their chemical structure when forming the thermally conductive material. Furthermore, any component that forms the thermally conductive material is considered to be a solid content even if it is in a liquid state.

[0046] [Epoxy Compound] The composition of the present invention comprises an epoxy compound. An epoxy compound is a compound having at least one epoxy group (oxiranyl group) in one molecule. The epoxy group is a group obtained by removing one or more hydrogen atoms (preferably one hydrogen atom) from an oxirane ring. If possible, the epoxy group may further have a substituent (such as a linear or branched alkyl group having 1 to 5 carbon atoms).

[0047] The number of epoxy groups that the epoxy compound has is preferably 2 or more, more preferably 2 to 1,000, and even more preferably 2 to 40, in one molecule.

[0048] The molecular weight of the epoxy compound is preferably 150 or more, more preferably 300 or more, and the upper limit is preferably 100,000 or less, more preferably 10,000 or less. When the molecular weight has a molecular weight distribution, the molecular weight is a weight average molecular weight. In this specification, the number average molecular weight and weight average molecular weight are weight average molecular weights determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0049] The epoxy group content of the epoxy compound is preferably 2.0 to 20.0 mmol / g, more preferably 5.0 to 15.0 mmol / g. The epoxy group content refers to the number of epoxy groups contained in 1 g of the epoxy compound. The epoxy compound also preferably has an aromatic ring group (preferably an aromatic hydrocarbon ring group).

[0050] The epoxy compound may or may not exhibit liquid crystallinity. That is, the epoxy compound may be a liquid crystal compound, or in other words, a liquid crystal compound having an epoxy group. Examples of the epoxy compound (which may be a liquid crystalline epoxy compound) include a compound having at least a partial rod-like structure (rod-like compound) and a compound having at least a partial discotic structure (discotic compound). The rod-shaped compounds and discotic compounds will be described in detail below.

[0051] (rod-shaped compound) Examples of epoxy compounds that are rod-shaped compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitriles. In addition to the low molecular weight compounds described above, high molecular weight compounds can also be used. The high molecular weight compounds are polymerized low molecular weight rod-shaped compounds having reactive groups. A preferred rod-shaped compound is a rod-shaped compound represented by the following formula (XXI). Formula (XXI):Q 1 -L 111 -A 111 -L 113 -ML 114 -A 112 -L 112 -Q 2

[0052] In formula (XXI), Q 1 and Q 2 are each independently an epoxy group, and L 111 , L 112 , L 113 and L 114 A each independently represents a single bond or a divalent linking group. 111 and A 112 each independently represents a divalent linking group (spacer group) having 1 to 20 carbon atoms. M represents a mesogenic group. Q 1 and Q 2 The epoxy group may or may not have a substituent.

[0053] In formula (XXI), L 111 , L 112 , L 113 and L 114 each independently represents a single bond or a divalent linking group. L 111 , L 112 , L 113 and L 114The divalent linking groups represented by the formula (I) are each independently -O-, -S-, -CO-, -NR 112 -, -CO-O-, -O-CO-O-, -CO-NR 112 -, -CH2-O-, -O-CO-NR 112 - and -NR 112 -CO-NR 112 - is preferably a divalent linking group selected from the group consisting of 112 is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. Among them, L 113 and L 114 are each independently preferably —O—. L 111 and L 112 are each independently preferably a single bond.

[0054] In formula (XXI), A 111 and A 112 each independently represents a divalent linking group having 1 to 20 carbon atoms. The divalent linking group may contain heteroatoms such as non-adjacent oxygen atoms and sulfur atoms. Among these, alkylene groups, alkenylene groups, and alkynylene groups having 1 to 12 carbon atoms are preferred. The alkylene groups, alkenylene groups, and alkynylene groups may or may not have an ester group. The divalent linking group is preferably linear, and may or may not have a substituent, such as a halogen atom (fluorine atom, chlorine atom, or bromine atom), a cyano group, a methyl group, or an ethyl group. Among them, A 111 and A 112 are each independently preferably an alkylene group having 1 to 12 carbon atoms, more preferably a methylene group.

[0055] In formula (XXI), M represents a mesogenic group. Examples of the mesogenic group include known mesogenic groups. Among them, a group represented by the following formula (XXII) is preferred. Formula (XXII): -(W 1 -L115 ) n -W 2 -

[0056] In formula (XXII), W 1 and W 2 L each independently represents a divalent cyclic alkylene group, a divalent cyclic alkenylene group, an arylene group, or a divalent heterocyclic group. 115 represents a single bond or a divalent linking group, and n represents an integer of 1 to 4.

[0057] W 1 and W 2 Examples of the cyclohexanediyl include 1,4-cyclohexenediyl, 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, and pyridazine-3,6-diyl. In the case of 1,4-cyclohexanediyl, either the trans or cis structural isomer may be used, or a mixture of these isomers may be used in any proportion. Of these, the trans isomer is preferred. W 1 and W 2 may each have a substituent. Examples of the substituent include the groups exemplified in the above-mentioned substituent group Y, and more specific examples include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, and a propyl group), an alkoxy group having 1 to 10 carbon atoms (for example, a methoxy group and an ethoxy group), an acyl group having 1 to 10 carbon atoms (for example, a formyl group and an acetyl group), an alkoxycarbonyl group having 1 to 10 carbon atoms (for example, a methoxycarbonyl group and an ethoxycarbonyl group), an acyloxy group having 1 to 10 carbon atoms (for example, an acetyloxy group and a propionyloxy group), a nitro group, a trifluoromethyl group, and a difluoromethyl group. W 1 If there are multiple W 1 may be the same or different.

[0058] In formula (XXII), L 115 represents a single bond or a divalent linking group. 115 The divalent linking group represented by the formula (I) is the same as the above-mentioned L 111 ~L 114 Specific examples of the divalent linking group include -CO-O- and -CH2-O-. L 115 If there are multiple L 115 may be the same or different.

[0059] Preferred examples of the basic skeleton of the mesogenic group represented by formula (XXII) are shown below: The mesogenic group may have a substituent on the skeleton.

[0060] [ka]

[0061] [ka]

[0062] Among these, the mesogenic group preferably has a biphenyl skeleton, since the resulting thermally conductive material has better thermal conductivity. The compound represented by formula (XXI) can be synthesized by referring to the method described in JP-A-11-513019 (WO97 / 00600). The rod-like compound may be a monomer having a mesogen group as described in JP-A-11-323162 and Japanese Patent No. 4118691.

[0063] In addition, in the compound represented by formula (XXI), "Q 1 -L 111 -" and "-L 112 -Q 2 Also preferred are compounds in which one or both of the groups are replaced with a diglycidylamino group.

[0064] Among these, the rod-like compound is preferably a compound represented by formula (E1).

[0065] [ka]

[0066] In formula (E1), L E1 each independently represents a single bond or a divalent linking group. Among them, L E1 is preferably a divalent linking group. The divalent linking group is preferably -O-, -S-, -CO-, -NH-, -CH=CH-, -C≡C-, -CH=N-, -N=N-, an optionally substituted alkylene group, or a group consisting of a combination of two or more of these, and more preferably -O-alkylene group-. The alkylene group may be linear, branched, or cyclic, and is preferably a linear alkylene group having 1 to 2 carbon atoms. Multiple Ls E1 may be the same or different.

[0067] In formula (E1), L E2 are each independently a single bond, -CH=CH-, -CO-O-, -C(-CH3)=CH-, -CH=N-, -N=N-, -C≡C-, -N=N + (-O - )-, -CH=N + (-O - )-, -CH=CH-CO- or -CH=C(-CN)-. Among them, L E2 are each independently preferably a single bond or —CO—O—. L E2 If there are multiple L E2 may be the same or different.

[0068] In formula (E1), L E3each independently represents a single bond or an optionally substituted 5- or 6-membered aromatic ring group, an optionally substituted 5- or 6-membered non-aromatic ring group, or a polycyclic group consisting of these rings. L E3 Examples of aromatic and non-aromatic ring groups represented by the formula (I) include optionally substituted 1,4-cyclohexanediyl, 1,4-cyclohexenediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, and pyridazine-3,6-diyl groups. In the case of a 1,4-cyclohexanediyl group, it may be either a trans or cis structural isomer, or a mixture of any proportions. Of these, the trans isomer is preferred. Among them, L E3 is preferably a single bond, a 1,4-phenylene group or a 1,4-cyclohexenediyl group. L E3 The substituents on the group represented by the formula (I) are each independently preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group or an acetyl group, more preferably an alkyl group (preferably a methyl group). When a plurality of substituents are present, the substituents may be the same or different. L E3 If there are multiple L E3 may be the same or different.

[0069] In formula (E1), pe represents an integer of 0 or more. If pe is an integer greater than or equal to 2, there are multiple (-L E3 -L E2 -) may be the same or different. Among these, pe is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0070] In formula (E1), L E4each independently represents a substituent. The substituents are each independently preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group or an acetyl group, more preferably an alkyl group (preferably a methyl group). Multiple Ls E4 may be the same or different. In addition, when le, which will be described later, is an integer of 2 or more, the same (L E4 ) le There are multiple L's in E4 may be the same or different.

[0071] In formula (E1), each le independently represents an integer of 0 to 4. In particular, it is preferable that each le is independently 0 to 2. Multiple le's may be the same or different.

[0072] In addition, in the compound represented by formula (E1), two "epoxy groups -L E1 Also preferred are compounds in which one or both of the "-" groups are replaced with a diglycidylaminoalkylene group (preferably a diglycidylaminomethylene group).

[0073] The rod-like compound preferably has a biphenyl skeleton, since the resulting thermally conductive material has better thermal conductivity. In other words, the epoxy compound preferably has a biphenyl skeleton, and in this case, the epoxy compound is preferably a rod-shaped compound.

[0074] (discotic compounds) The discotic epoxy compound has at least a partial discotic structure. The discotic structure has at least an alicyclic or aromatic ring. In particular, when the discotic structure has an aromatic ring, the discotic compound can form a columnar structure by forming a stacking structure due to intermolecular π-π interactions. Examples of the discotic structure include the triphenylene structure described in Angew. Chem. Int. Ed. 2012, 51, 7990-7993 and JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-002220 and JP-A-2010-244038.

[0075] If a discotic compound is used as the epoxy compound, a thermally conductive material with high thermal conductivity can be obtained. The reason for this is thought to be that while rod-shaped compounds can only conduct heat linearly (one-dimensionally), discotic compounds can conduct heat planarly (two-dimensionally) in the normal direction, which increases the number of heat conduction paths and improves thermal conductivity.

[0076] The discotic compound preferably has three or more epoxy groups. A cured product of a composition containing a discotic compound having three or more epoxy groups tends to have a high glass transition temperature and high heat resistance. The number of epoxy groups possessed by the discotic compound is preferably 8 or less, more preferably 6 or less. The lower limit is preferably 2 or more, more preferably 3 or more.

[0077] Examples of the discotic compound include compounds in which at least one (preferably three or more) of the terminals is an epoxy group, such as those described in C. Destrade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981); Quarterly Review of Chemistry, No. 22, edited by the Chemical Society of Japan, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., page 1794 (1985); J. Zhang et al., J. Am. Chem. Soc., vol. 116, page 2655 (1994) and Japanese Patent No. 4592225. Examples of the discotic compound include the triphenylene structure described in Angew. Chem. Int. Ed. 2012, 51, 7990-7993 and JP-A-7-306317, and the trisubstituted benzene structure described in JP-A-2007-002220 and JP-A-2010-244038, in which at least one (preferably three or more) of the terminals is an epoxy group.

[0078] As the discotic compound, a compound represented by any one of the following formulas (D1) to (D16) is preferred, from the viewpoint of providing a thermally conductive material with better thermal conductivity. In addition, in the formulas (D1) to (D16), "-LQ" represents "-LQ", and "QL-" represents "QL-".

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] In the formulae (D1) to (D15), L represents a divalent linking group. From the viewpoint of achieving better thermal conductivity of the thermally conductive material, L is preferably each independently a group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O-, -S-, and combinations thereof, and more preferably a group combining two or more groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O-, and -S-. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms. The alkylene group, the alkenylene group, and the arylene group may have a substituent (preferably an alkyl group, a halogen atom, cyano, an alkoxy group, an acyloxy group, or the like).

[0084] Examples of L include groups represented by L101 to L143. In the following, the left bond is bonded to the central structure (hereinafter also simply referred to as the "central ring") of the compound represented by any one of formulas (D1) to (D15), and the right bond is bonded to Q. AL represents an alkylene group or an alkenylene group, and AR represents an arylene group. The alkylene group represented by AL may be linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 12. The alkenylene group represented by AL may be linear or branched. The number of carbon atoms in the alkenylene group is preferably 2 to 12. The arylene group represented by AR may be monocyclic or polycyclic. The number of ring atoms in the arylene group is preferably 6 to 12.

[0085] L101:-AL-CO-O-AL- L102:-AL-CO-O-AL-O- L103:-AL-CO-O-AL-O-AL- L104:-AL-CO-O-AL-O-CO- L105:-CO-AR-O-AL- L106:-CO-AR-O-AL-O- L107:-CO-AR-O-AL-O-CO- L108:-CO-NH-AL- L109:-NH-AL-O- L110:-NH-AL-O-CO- L111:-O-AL- L112:-O-AL-O- L113:-O-AL-O-CO-

[0086] L114:-O-AL-O-CO-NH-AL- L115:-O-AL-S-AL- L116:-O-CO-AL-AR-O-AL-O-CO- L117:-O-CO-AR-O-AL-CO- L118:-O-CO-AR-O-AL-O-CO- L119:-O-CO-AR-O-AL-O-AL-O-CO- L120:-O-CO-AR-O-AL-O-AL-O-AL-O-CO- L121:-S-AL- L122:-S-AL-O- L123:-S-AL-O-CO- L124:-S-AL-S-AL- L125:-S-AR-AL- L126:-O-CO-AL- L127:-O-CO-AL-O- L128:-O-CO-AR-O-AL- L129:-O-CO- L130:-O-CO-AR-O-AL-O-CO-AL-S-AR- L131:-O-CO-AL-S-AR- L132:-O-CO-AR-O-AL-O-CO-AL-S-AL- L133:-O-CO-AL-S-AR- L134:-O-AL-S-AR- L135:-AL-CO-O-AL-O-CO-AL-S-AR- L136:-AL-CO-O-AL-O-CO-AL-S-AL- L137:-O-AL-O-AR- L138:-O-AL-O-CO-AR- L139:-O-AL-NH-AR- L140:-O-CO-AL-O-AR- L141:-O-CO-AR-O-AL-O-AR- L142:-AL-CO-O-AR- L143:-AL-CO-O-AL-O-AR-

[0087] In the formulae (D1) to (D15), each Q independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified in the above-mentioned substituent group Y. More specifically, examples of the substituent include the above-mentioned reactive functional groups, halogen atoms, isocyanate groups, cyano groups, unsaturated polymerizable groups, epoxy groups, oxetanyl groups, aziridinyl groups, thioisocyanate groups, aldehyde groups, and sulfo groups. However, when Q is a group other than an epoxy group, Q is preferably stable against the epoxy group. In the formulas (D1) to (D15), one or more (preferably two or more) Qs represent an epoxy group. In particular, from the viewpoint of achieving superior thermal conductivity of the thermal conductive material, it is preferable that all Qs represent an epoxy group. From the viewpoint of the stability of the epoxy group, it is preferable that the compounds represented by formulae (D1) to (D15) do not have —NH—.

[0088] Among them, the discotic compound is preferably a compound represented by formula (D4) from the viewpoint of providing a thermally conductive material with superior thermal conductivity. In other words, the central ring of the discotic compound is preferably a triphenylene ring. As the compound represented by formula (D4), a compound represented by formula (XI) is preferred from the viewpoint of providing a thermally conductive material with better thermal conductivity.

[0089] [ka]

[0090] In formula (XI), R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently *-X 11 -L 11 -P 11 or *-X 12 -L 12 -Y 12 Represents. In addition, * indicates the bonding position to the triphenylene ring. R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Of these, two or more are *-X 11 -L 11 -P 11 and 3 or more are *-X 11 -L 11 -P 11 It is preferable that: Among them, from the viewpoint of superior thermal conductivity of thermal conductive materials, R 11 and R 12 One or more of the following, R 13 and R 14 One or more of the following and R 15 and R 16 At least one of the following is *-X 11 -L 11 -P 11 It is preferable that: R 11 , R 12 , R 13 , R 14 , R 15 and R 16 But all *-X 11 -L 11 -P 11 It is more preferable that R 11 , R 12 , R 13 , R 14 , R 15 and R 16 It is more preferable that they are all the same.

[0091] X 11 each independently represents a single bond, -O-, -CO-, -NH-, -O-CO-O-, -O-CO-NH-, -O-CO-S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-NH-, -NH-CO-S-, -S-, -S-CO-NH- or -S-CO-S-. Among them, X 11are each independently preferably -O-, -O-CO-O-, -O-CO-NH-, -CO-O- or -CO-NH-, more preferably -O-, -CO-O- or -O-CO-NH-, and still more preferably -CO-O-.

[0092] L 11 each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-O-, -S-, -NH-, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 7 carbon atoms), an arylene group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 14 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and groups formed from a combination thereof. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptylene group. Examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, and an anthracenylene group, with a 1,4-phenylene group being preferred.

[0093] The alkylene group and the arylene group may each have a substituent. The number of the substituent is preferably 1 to 3, and more preferably 1. The substitution position of the substituent is not particularly limited. The substituent is preferably a halogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkylene group and the arylene group are preferably unsubstituted, and the alkylene group is particularly preferably unsubstituted.

[0094] -X 11 -L 11 Examples of - include L101 to L143, which are examples of L mentioned above.

[0095] P 11 represents an epoxy group. The epoxy group may or may not have a substituent.

[0096] X 12 is X 11 The same applies to the preferable conditions. L 12 L 11 The same applies to the preferable conditions. -X 12 -L 12 Examples of - include L101 to L143, which are examples of L mentioned above.

[0097] Y 12 represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 1 to 20 carbon atoms, or a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 1 to 20 carbon atoms in which one or more methylene groups have been substituted with -O-, -S-, -NH-, -N(CH3)-, -CO-, or -CO-O-. Y 12 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms in which one or more methylene groups are substituted by -O-, -S-, -NH-, -N(CH3)-, -CO- or -CO-O-, when Y 12 One or more hydrogen atoms contained in may be substituted with a halogen atom.

[0098] Examples of the compound represented by formula (XI) include compounds described in paragraphs

[0028] to

[0036] of JP-A No. 7-281028, paragraphs

[0016] to

[0018] of JP-A No. 7-306317, paragraphs

[0016] to

[0018] of JP-A No. 2005-156822, paragraphs

[0067] to

[0072] of JP-A No. 2006-301614, and pages 330 to 333 of the Liquid Crystal Handbook (published by Maruzen Co., Ltd. in 2000), in which at least one (preferably three or more) of the terminals is an epoxy group.

[0099] The compound represented by formula (XI) can be synthesized according to the methods described in JP-A Nos. 7-306317, 7-281028, 2005-156822, and 2006-301614.

[0100] In addition, from the viewpoint of obtaining a thermally conductive material with better thermal conductivity, the discotic compound is also preferably a compound represented by formula (D16).

[0101] [ka]

[0102] In formula (D16), A 2X , A 3X and A 4X Each independently represents -CH= or -N=. 2X , A 3X and A 4X It is preferable that all of them are -CH= or all of them are -N=. That is, A 2X , A 3X and A 4X It is preferable that the six-membered ring containing the following is a benzene ring or a triazine ring. R 17X , R 18X and R 19X are each independently *-X 211X -(Z 21X -X 212X ) n21X -L 21X -Q. * indicates the bonding position to the central ring. X 211X and X 212X each independently represents a single bond, -O-, -CO-, -NH-, -O-CO-O-, -O-CO-S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-O-, -NH-CO-NH-, -NH-CO-S-, -S- or -S-CO-S-. Z 21X each independently represents a 5- or 6-membered aromatic ring group, or a 5- or 6-membered non-aromatic ring group. L 21Xrepresents a single bond or a divalent linking group. Q has the same meaning as Q in formulae (D1) to (D15), and the preferred range is also the same. In formula (D16), of the multiple Qs, at least one (preferably all) Qs represent an epoxy group. n21X represents an integer of 0 to 3. When n21X is 2 or more, a plurality of n21X exists (Z 21X -X 212X ) may be the same or different.

[0103] The compound represented by formula (D16) is preferably a compound represented by formula (XII).

[0104] [ka]

[0105] In formula (XII), A 2 , A 3 and A 4 Each independently represents -CH= or -N=. 2 , A 3 and A 4 It is preferable that all of them are -CH= or all of them are -N=. That is, A 2 , A 3 and A 4 It is preferable that the six-membered ring containing the following is a benzene ring or a triazine ring.

[0106] R 17 , R 18 and R 19 are each independently *-X 211 -(Z 21 -X 212 ) n21 -L 21 -P 21 or *-X 221 -(Z 22 -X 222 ) n22 -Y 22 * indicates the bonding position to the central ring. R 17 , R 18 and R19 At least two of them are *-X 211 -(Z 21 -X 212 ) n21 -L 21 -P 21 From the viewpoint of superior thermal conductivity of the thermal conductive material, R 17 , R 18 and R 19 are all *-X 211 -(Z 21 -X 212 ) n21 -L 21 -P 21 It is preferable that: In addition, R 17 , R 18 and R 19 However, it is preferable that they are all the same.

[0107] X 211 , X 212 , X 221 and X 222 each independently represents a single bond, -O-, -CO-, -NH-, -O-CO-O-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-O-, -NH-CO-NH-, -NH-CO-S-, -S-, -S-CO-O- or -S-CO-S-. Among them, X 211 , X 212 , X 221 and X 222 are each independently preferably a single bond, -NH-, -O- or -CO-O-.

[0108] Z 21 and Z 22 each independently represents a 5- or 6-membered aromatic ring group or a 5- or 6-membered non-aromatic ring group, such as a benzene ring group (1,4-phenylene group, 1,3-phenylene group, etc.) and an aromatic heterocyclic group.

[0109] The aromatic ring group and the non-aromatic ring group may have a substituent. When the aromatic ring group and the non-aromatic ring group have a substituent, the number of the substituents is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. The substitution position of the substituent is not particularly limited. The substituent is preferably a halogen atom or a methyl group. The aromatic ring group and the non-aromatic ring group are also preferably unsubstituted. Furthermore, as the substituent, "-X 212 -L 21 -P 21 " may have a group represented by the formula:

[0110] Examples of the aromatic heterocyclic group include the following aromatic heterocyclic groups.

[0111] [ka]

[0112] In the formula, * represents X 211 or X 221 ** represents the binding site to X 212 or X 222 A represents the binding site. 41 and A 42 each independently represents a methine group or a nitrogen atom. 4 represents an oxygen atom, a sulfur atom or an imino group. A 41 and A 42 At least one of X is preferably a nitrogen atom, and more preferably both are nitrogen atoms. 4 is preferably an oxygen atom.

[0113] When n21 and n22, which will be described later, are 2 or more, there are multiple 21 -X 212 ) and (Z 22 -X 222 ) may be the same or different.

[0114] L 21 each independently represents a single bond or a divalent linking group, and L in the above formula (XI) 11 It is synonymous with L.21 is preferably -O-, -CO-O-, -S-, -NH-, an alkylene group (having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 7 carbon atoms), an arylene group (having preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms), or a group formed from a combination thereof.

[0115] When n22 (described later) is 1 or more, -X 212 -L 21 Examples of - include L101 to L143, which are examples of L in the above formulae (D1) to (D15). However, in L101 to L143, the left bond is bonded to the central structure of the compound (hereinafter also simply referred to as "central ring"), and the right bond is bonded to P 21 Combine with.

[0116] P 21 represents an epoxy group. The epoxy group may or may not have a substituent.

[0117] Y 22 each independently represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 1 to 20 carbon atoms, in which one or more methylene groups are substituted with -O-, -S-, -NH-, -N(CH3)-, -CO-, or -CO-O-; and Y in formula (XI) 12 The same definition and preferred range are also the same.

[0118] n21 and n22 each independently represent an integer of 0 to 3, and from the viewpoint of more excellent thermal conductivity, an integer of 1 to 3 is preferable. 2 , A 3 and A 4 are both -CH=, it is more preferable that n21 and n22 each independently represent an integer of 2 to 3, and A 2 , A 3 and A 4When both are -N=, it is more preferable that n21 and n22 each independently represent 1.

[0119] Preferred examples of the discotic compound include the following compounds:

[0120] [ka]

[0121] [ka]

[0122] [ka] JPEG0007814328000018.jpg47118JPEG0007814328000019.jpg47118

[0123] [ka] JPEG0007814328000021.jpg49118JPEG0007814328000022.jpg47118

[0124] [ka] JPEG0007814328000024.jpg47118JPEG0007814328000025.jpg47118

[0125] [ka] JPEG0007814328000027.jpg47118 JPEG0007814328000028.jpg43116

[0126] In the following structural formula, R represents -X 212 -L 21 -P 21 Represents.

[0127] [ka]

[0128] [ka]

[0129] For details and specific examples of the compound represented by formula (XII), reference can be made to the compounds described in paragraphs

[0013] to

[0077] of JP2010-244038A, in which at least one (preferably three or more) of the terminals are epoxy groups, the contents of which are incorporated herein by reference.

[0130] The compound represented by formula (XII) can be synthesized according to the methods described in JP-A Nos. 2010-244038, 2006-076992, and 2007-002220.

[0131] From the viewpoint of reducing the electron density, strengthening stacking, and facilitating the formation of columnar aggregates, the discotic compound is preferably a compound having a hydrogen-bonding functional group, such as -O-CO-NH-, -CO-NH-, -NH-CO-NH-, and -NH-CO-S-.

[0132] (Other epoxy compounds) The epoxy compound may contain other epoxy compounds in addition to the above-mentioned epoxy compounds. Other epoxy compounds that can be used include, for example, compounds in which the phenolic hydroxyl group in the compound represented by the above-mentioned formula (Z), the compound represented by formula (Z1), or the compound represented by formula (Z2) is replaced with an epoxy-containing group. The epoxy-containing group is a group that is an epoxy group itself or a monovalent group that contains an epoxy group as a portion thereof. The monovalent group partially containing an epoxy group is a group having one or more (preferably 1 to 8) epoxy groups within the entire group. The monovalent group containing an epoxy group as a part thereof is "-(divalent hydrocarbon group) M1 -(-O-divalent hydrocarbon group-) M2 -epoxy group" is preferred. In the above group, M1 represents 0 or 1. M2 represents an integer of 1 or more (preferably 1 to 10). Examples of the divalent hydrocarbon group in the above group include alkylene groups (preferably having 1 to 6 carbon atoms), alkenylene groups (-CH=CH-, etc., preferably having 2 to 6 carbon atoms), alkynylene groups (-C≡C-, etc., preferably having 2 to 6 carbon atoms), arylene groups (phenylene group, etc., preferably having 6 to 15 carbon atoms), and groups combining these. The divalent hydrocarbon group may or may not have a substituent, and the divalent hydrocarbon group may further have an epoxy-containing group as a substituent. The divalent hydrocarbon groups, which may be present in plurality, may be the same or different.

[0133] Other examples of the epoxy compound include epoxy compounds represented by formula (DN).

[0134] [ka]

[0135] In formula (DN), n DN represents an integer of 0 or more, preferably 0 to 5, and more preferably 1. R DN represents a single bond or a divalent linking group. The divalent linking group is preferably -O-, -CO-O-, -S-, an alkylene group (preferably having 1 to 10 carbon atoms), an arylene group (preferably having 6 to 20 carbon atoms), or a combination thereof, more preferably an alkylene group, and even more preferably a methylene group.

[0136] Other examples of the epoxy compound include the epoxy compound represented by formula (E2). (V-) 4-UC(-W) U (E2)

[0137] In formula (E2), C represents a carbon atom.

[0138] In formula (E2), U represents an integer of 3 or 4. In formula (E2), the "U" in "4-U" indicating the number of Vs and the "U" indicating the number of Ws have the same value. In other words, formula (E2) is "VC(-W)3" or "C(-W)4".

[0139] In formula (E2), V represents a substituent not having an epoxy group or a hydrogen atom. The substituent not having an epoxy group is a substituent other than an epoxy group, and does not contain an epoxy group even as a part of the substituent. Examples of the substituent not having an epoxy group include groups selected from the substituent group Y, excluding epoxy groups and groups partially containing an epoxy group. The substituent not having an epoxy group is preferably an alkyl group, more preferably a linear or branched alkyl group, and preferably has 1 to 5 carbon atoms.

[0140] In formula (E2), W represents an epoxy-containing group. The epoxy-containing group is a group that is an epoxy group itself or a monovalent group that contains an epoxy group as a portion thereof. The monovalent group partially containing an epoxy group is a group having one or more (preferably 1 to 8) epoxy groups within the entire group. The monovalent group containing an epoxy group as a part thereof is "-(divalent hydrocarbon group) M1 -(-O-divalent hydrocarbon group-) M2-epoxy group" is preferred. In the above group, M1 represents 0 or 1. M2 represents an integer of 1 or more (preferably 1 to 10). Examples of the divalent hydrocarbon group in the above group include alkylene groups (preferably having 1 to 6 carbon atoms), alkenylene groups (-CH=CH-, etc., preferably having 2 to 6 carbon atoms), alkynylene groups (-C≡C-, etc., preferably having 2 to 6 carbon atoms), arylene groups (phenylene group, etc., preferably having 6 to 15 carbon atoms), and groups combining these. The divalent hydrocarbon group may or may not have a substituent, and the divalent hydrocarbon group may further have an epoxy-containing group as a substituent. The divalent hydrocarbon groups, which may be present in plurality, may be the same or different. A plurality of Ws present in formula (E2) may be the same or different.

[0141] Other epoxy compounds include compounds in which the epoxy group is fused to a ring, such as 3,4:8,9-diepoxybicyclo[4.3.0]nonane.

[0142] Other epoxy compounds include, for example, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, and bisphenol AD-type epoxy compounds, which are glycidyl ethers of bisphenol A, F, S, AD, and the like; hydrogenated bisphenol A-type epoxy compounds and hydrogenated bisphenol AD-type epoxy compounds; phenol novolac-type glycidyl ethers (phenol novolac-type epoxy compounds), cresol novolac-type glycidyl ethers (cresol novolac-type epoxy compounds), and bisphenol A novolac-type glycidyl ethers; dicyclopentadiene-type glycidyl ethers (dicyclopentadiene-type epoxy compounds); dihydroxypentadiene-type glycidyl ethers (dihydroxypentadiene-type epoxy compounds); polyhydroxybenzene-type glycidyl ethers (polyhydroxybenzene-type epoxy compounds) such as glycidyl ethers of dihydroxybenzenes such as resorcinol; benzenepolycarboxylic acid-type glycidyl esters (benzenepolycarboxylic acid-type epoxy compounds); trisphenolmethane-type epoxy compounds; phenoxy resins; and acrylic resins having epoxy groups on their side chains. A compound in which one or more of the glycidyl ether groups and / or glycidyl ester groups in each of the above-mentioned compounds are replaced with a diglycidylamino group or a diglycidylaminoalkylene group (such as a diglycidylaminomethylene group) may be used as the epoxy compound. Each of the above compounds may have a substituent. For example, the aromatic ring group, cycloalkane ring group, and / or alkylene group contained in each of the above compounds may have a substituent other than a glycidyl ether group, a glycidyl ester group, a diglycidylamino group, and / or a diglycidylaminoalkylene group.

[0143] The epoxy compounds may be used alone or in combination of two or more. The content of the epoxy compound is preferably 1.0 to 90.0 mass %, more preferably 3.0 to 50.0 mass %, still more preferably 5.0 to 40.0 mass %, and particularly preferably 5.0 to 10.0 mass %, based on the total solid content of the composition.

[0144] [Relationship between phenolic compounds and epoxy compounds] It is preferable that at least one of the requirements that the phenolic compound contains a phenolic compound having a triazine skeleton (requirement 1) and that the epoxy compound contains an epoxy compound having a triazine skeleton (requirement 2) is satisfied; it is more preferable that either the requirement that the phenolic compound contains a phenolic compound having a triazine skeleton (requirement 1) and that the epoxy compound contains an epoxy compound having a triazine skeleton (requirement 2) is satisfied; and it is even more preferable that the phenolic compound contains a phenolic compound having a triazine skeleton (requirement 1) and that the epoxy compound does not contain an epoxy compound having a triazine skeleton (requirement 2). The composition may satisfy only requirement 1, may satisfy only requirement 2, or may satisfy both requirements 1 and 2.

[0145] The phenol compound and epoxy compound "having a triazine skeleton" means that the compound has one or more (for example, 1 to 5) triazine ring groups. Examples of the phenol compound having a triazine skeleton include the compounds represented by the formula (Z), the compounds represented by the formula (Z1), and the compounds represented by the formula (Z2). As the epoxy compound having a triazine skeleton, for example, in the compound represented by formula (D16), A 2X , A 3X and A 4X In the compound represented by formula (XII), A 2 , A 3 and A 4 are each -N=; a compound in which the phenolic hydroxyl group in formula (Z) is replaced with an epoxy-containing group; a compound in which the phenolic hydroxyl group in formula (Z1) is replaced with an epoxy-containing group; and a compound in which the phenolic hydroxyl group in formula (Z2) is replaced with an epoxy-containing group.

[0146] When the phenolic compound contains a phenolic compound having a triazine skeleton (when requirement 1 is satisfied), the content of the phenolic compound having a triazine skeleton is preferably more than 0% by mass and not more than 100% by mass, more preferably 30 to 100% by mass, even more preferably 60 to 100% by mass, and particularly preferably 90 to 100% by mass, based on the total mass of the phenolic compounds. Note that when the composition contains an epoxy compound, and the epoxy compound contains an epoxy compound having a triazine skeleton (when requirement 2 is satisfied), it is also preferable that the content of the phenolic compound having a triazine skeleton is outside the above-mentioned preferred range. When the epoxy compound contains an epoxy compound having a triazine skeleton (when requirement 2 is satisfied), the content of the epoxy compound having a triazine skeleton is preferably more than 0% by mass and not more than 100% by mass, more preferably 30 to 100% by mass, even more preferably 60 to 100% by mass, and particularly preferably 90 to 100% by mass, based on the total mass of the epoxy compound. Note that when the phenol compound contains a phenol compound having a triazine skeleton (when requirement 1 is satisfied), it is also preferable that the content of the epoxy compound having a triazine skeleton is outside the above-mentioned preferred range.

[0147] It is also preferred that at least a part of the phenol compound and the epoxy compound is a compound other than a compound having a triazine skeleton. All or part of the phenol compounds may be compounds other than those having a triazine skeleton, and all or part of the epoxy compounds may be compounds other than those having a triazine skeleton. From the viewpoint of adjusting the crosslink density and further improving the effects of the present invention, the total content of the phenol compound having a triazine skeleton and the epoxy compound having a triazine skeleton is preferably more than 0 mass% and less than 100 mass%, more preferably 1 to 90 mass%, and even more preferably 5 to 80 mass%, based on the total content of all phenol compounds and all epoxy compounds.

[0148] The total content of the epoxy compound and the phenol compound is preferably from 3 to 90 mass %, more preferably from 5 to 50 mass %, and even more preferably from 7 to 40 mass %, based on the total solid content of the composition.

[0149] The ratio of the number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenol compound to the total number of epoxy groups contained in the epoxy compound (number of epoxy groups / number of hydroxyl groups) is preferably 3 / 97 to 97 / 3, more preferably 30 / 70 to 70 / 30, still more preferably 40 / 60 to 60 / 40, and particularly preferably 45 / 55 to 55 / 45. In other words, the ratio of the content of the phenol compound to the content of the epoxy compound is preferably such that the above-mentioned "number of epoxy groups / number of phenolic hydroxyl groups" falls within the above-mentioned range.

[0150] The equivalent ratio (number of epoxy groups / number of active hydrogen atoms) of the epoxy group of the epoxy compound to the active hydrogen atoms (which may be active hydrogen atoms derived from phenolic hydroxyl groups or active hydrogen atoms of other active hydrogen-containing compounds) is preferably 3 / 97 to 97 / 3, more preferably 30 / 70 to 70 / 30, still more preferably 40 / 60 to 60 / 40, and particularly preferably 45 / 55 to 55 / 45.

[0151] [Agglomerated boron nitride] The compositions of the present invention include aggregated boron nitride. Agglomerated boron nitride refers to secondary agglomerated particles formed by agglomerating primary particles of boron nitride (for example, scaly boron nitride). The average particle size of the aggregated boron nitride is 20 μm or more, preferably 30 μm or more, and more preferably 40 μm or more, and the upper limit is preferably 500 μm or less, more preferably 300 μm or less, even more preferably 200 μm or less, and particularly preferably 100 μm or less. "Particle size" refers to the average particle size of particles measured by the following method. The average particle size can be measured using a scanning electron microscope (SEM) or a laser diffraction particle size distribution analyzer. As the scanning electron microscope, for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. The maximum length (Dmax: the maximum length at two points on the outline of the particle image) and the maximum perpendicular length (DV-max: the shortest distance between two lines parallel to the maximum length when the image is sandwiched between them) of a particle image obtained using a scanning electron microscope were measured, and the geometric mean value (Dmax x DV-max) was calculated. 1 / 2 The particle sizes of 100 particles were measured by this method, and the arithmetic mean value was taken as the average particle size of the particles. The aggregated boron nitride preferably comprises a surface-modified aggregated boron nitride, as described below.

[0152] The agglomerated boron nitride may be surface treated. The surface treatment is intended to be a treatment different from the surface modification using a surface modifier, which will be described later. It is presumed that such treatment introduces functional groups onto the surface of the agglomerated boron nitride, making it easier for the agglomerated boron nitride to interact with phenolic compounds, epoxy compounds, and / or the surface modifiers described below, thereby further improving the thermal conductivity and peel strength of the resulting thermal conductive material. Examples of surface treatments include plasma treatments (vacuum plasma treatment, atmospheric pressure plasma treatment, aqua plasma treatment, etc.), ultraviolet irradiation treatment, corona treatment, electron beam irradiation treatment, ozone treatment, baking treatment, flame treatment, and oxidizing agent treatment. The oxidizing agent treatment may be carried out under acidic conditions or basic conditions (e.g., pH 12 or higher).

[0153] The aggregated boron nitride may be used alone or in combination of two or more kinds. The content of the aggregated boron nitride is preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total solid content of the composition, and the upper limit is preferably less than 100% by mass, more preferably 95% by mass or less, and even more preferably 80% by mass or less, based on the total solid content of the composition.

[0154] [Inorganic X] The composition of the present invention includes an inorganic substance X. The inorganic substance X means at least one selected from the group consisting of aluminum oxide and silicon dioxide. The average particle size of the inorganic substance X (the average particle size of aluminum oxide or the average particle size of silicon dioxide) is 0.30 μm or less, preferably less than 0.30 μm, more preferably 0.25 μm or less, even more preferably 0.20 μm or less, particularly preferably 0.15 μm or less. The lower limit is preferably 0.001 μm or more, more preferably 0.01 μm or more. The particle size is synonymous with the particle size of the aggregated boron nitride described above, and the measurement method is also the same. The inorganic substance X is preferably aluminum oxide or silicon dioxide, and more preferably surface-modified aluminum oxide or surface-modified silicon dioxide, which will be described later.

[0155] (aluminum oxide) The aluminum oxide may be in the form of particles or plates. Examples of particulate shapes include rice grain shapes, spherical shapes, cubic shapes, spindle shapes, scale shapes, aggregate shapes, and irregular shapes. The aluminum oxide may be aluminum oxide that is produced by oxidizing aluminum metal prepared as a non-oxide under environmental conditions. The aluminum oxide preferably contains surface-modified aluminum oxide, which will be described later.

[0156] (silicon dioxide) The silicon dioxide may be in the form of particles or plates. Examples of particulate shapes include rice grain shapes, spherical shapes, cubic shapes, spindle shapes, scale shapes, aggregate shapes, and irregular shapes, with spherical shapes being preferred. The silicon dioxide preferably includes surface-modified silicon dioxide, which will be described later.

[0157] [Other inorganic substances] The composition of the present invention may contain other inorganic substances in addition to the specific inorganic substances described above. The other inorganic substance is not particularly limited as long as it is a substance other than the specific inorganic substances described above. Examples of the other inorganic substance include known inorganic substances, and inorganic substances that have traditionally been used as inorganic fillers in thermally conductive materials may also be used. In other words, the other inorganic substance may contain at least one selected from the group consisting of aggregated boron nitride having an average particle size of less than 20 μm, aluminum oxide having an average particle size of more than 0.30 μm, and silicon dioxide having an average particle size of more than 0.30 μm. Among these, the other inorganic substance preferably contains at least one selected from the group consisting of aluminum oxide having an average particle size of more than 0.30 μm and silicon dioxide having an average particle size of more than 0.30 μm.

[0158] Other inorganic substances include, for example, inorganic nitrides and inorganic oxides. The inorganic substance may also be in the form of particles, films, or plates. Examples of particle shapes include rice grain shapes, spheres, cubes, spindle shapes, scales, aggregates, and irregular shapes. The other inorganic substance may include other surface-modified inorganic substances described below.

[0159] Examples of inorganic nitrides include boron nitride (BN), carbon nitride (CN), silicon nitride (SiN), gallium nitride (GaN), indium nitride (InN), aluminum nitride (AlN), chromium nitride (CrN), copper nitride (CuN), iron nitride (FeN), iron nitride (FeN), lanthanum nitride (LaN), lithium nitride (LiN), magnesium nitride (MgN), molybdenum nitride (MoN), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten nitride (WN), yttrium nitride (YN), and zirconium nitride (ZrN).

[0160] Examples of inorganic oxides include zirconium oxide (ZrO2), titanium oxide (TiO2), iron oxide (Fe2O3, FeO, Fe3O4), copper oxide (CuO, Cu2O), zinc oxide (ZnO), yttrium oxide (Y2O3), niobium oxide (Nb2O5), molybdenum oxide (MoO3), indium oxide (In2O3, In2O), tin oxide (SnO2), tantalum oxide (Ta2O5), tungsten oxide (WO3, W2O5), lead oxide (PbO, PbO2), bismuth oxide (Bi2O3), cerium oxide (CeO2, Ce2O3), antimony oxide (Sb2O3, Sb2O5), germanium oxide (GeO2, GeO), lanthanum oxide (La2O3), and ruthenium oxide (RuO2). It is also preferable that the inorganic oxide is different from the inorganic ion scavenger described below. The inorganic oxide may be an oxide that is produced when a metal prepared as a non-oxide is oxidized under environmental conditions. The other inorganic substances may be used alone or in combination of two or more.

[0161] The inorganic substance X may be used alone or in combination of two or more kinds. The content of the inorganic substance X is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total solid content of the composition. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 8% by mass or less, based on the total solid content of the composition.

[0162] The mass ratio of the content of aggregated boron nitride to the content of inorganic substance X (content of aggregated boron nitride / content of inorganic substance X) is preferably 0.6 to 99.0, more preferably 1.0 to 30.0, even more preferably 3.0 to 25.0, particularly preferably 5.0 to 25.0, and most preferably 7.0 to 25.0.

[0163] The content of other inorganic substances is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total solid content of the composition. The mass ratio of the content of aggregated boron nitride to the total content of other inorganic substances and inorganic substance X (content of aggregated boron nitride / total content of other inorganic substances and inorganic substance X) is preferably 1.0 to 50.0, more preferably 1.0 to 30.0, and even more preferably 1.0 to 10.0.

[0164] [Surface modifier, surface-modified aggregated boron nitride, and surface-modified inorganic substance X] The composition of the present invention may further contain a surface modifier as a component different from the above-mentioned components. The surface modifier is a component that modifies the surface of the aggregated boron nitride, inorganic substance X, and other inorganic substances. Surface modification refers to a state in which an organic substance is adsorbed to at least a portion of the surface of a specific inorganic substance. The form of adsorption is not particularly limited, as long as it is a bonded state. In other words, surface modification also includes a state in which an organic group obtained by partial detachment of the organic substance is bonded to the surface of the specific inorganic substance. The bond may be any of a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metallic bond. The surface modification may be performed so as to form a monolayer on at least a portion of the surface. A monolayer is a monolayer film formed by chemical adsorption of organic molecules and is known as a self-assembled monolayer (SAM). Note that, in this specification, the surface modification may be performed on only a portion or the entire surface of the specific inorganic substance.

[0165] (Surface modification specific inorganic substance) The surface-modified specific inorganic substance refers to a specific inorganic substance whose surface has been modified with a surface modifying agent (hereinafter also referred to as "surface-modified specific inorganic substance"). That is, the surface-modified specific inorganic substance is a material containing a specific inorganic substance and a surface modifier adsorbed onto the surface of the specific inorganic substance. That is, the specific inorganic substance may constitute the surface-modified specific inorganic substance together with the surface modifier adsorbed onto the surface of the specific inorganic substance. In the present invention, the composition may contain a surface-modified specific inorganic substance, and thereby the composition may contain a specific inorganic substance and a surface modifier. The specific inorganic substance in the composition may be partly or entirely a surface-modified specific inorganic substance together with the surface modifier. For example, in the composition, a specific inorganic substance may be present that constitutes the surface-modified specific inorganic substance of a part of the specific inorganic substance, and at the same time, a specific inorganic substance that is not involved in the formation of the surface-modified specific inorganic substance may be present. A part or all of the surface modifiers in the composition may constitute the surface-modified specific inorganic substance together with the specific inorganic substance. For example, in the composition, a part of the surface modifiers may constitute the surface-modified specific inorganic substance, and at the same time, a surface modifier that is not involved in the formation of the surface-modified specific inorganic substance may be present. The surface-modified specific inorganic substance can be formed, for example, by contacting a specific inorganic substance with a surface modifier. Specifically, the specific inorganic substance, the surface modifier, and other components constituting the composition of the present invention may be mixed together to form the surface-modified specific inorganic substance in the composition during the production process of the composition of the present invention. Alternatively, the specific inorganic substance and the surface modifier may be mixed in a solvent to prepare a mixed solution containing the surface-modified specific inorganic substance, and the surface-modified specific inorganic substance may be separated from the mixed solution by means of filtration or the like to obtain the separated surface-modified specific inorganic substance. The separated surface-modified specific inorganic substance may be used to prepare the composition of the present invention.

[0166] (Surface modifier) Examples of the surface modifier include known surface modifiers such as carboxylic acids such as long-chain alkyl fatty acids, organic phosphonic acids, organic phosphate esters, and organic silane molecules (silane coupling agents), as well as the surface modifiers described in JP 2009-502529 A, JP 2001-192500 A, and Japanese Patent No. 4694929.

[0167] The silane coupling agent may be, for example, a compound having a hydrolyzable group directly bonded to a Si atom. Examples of the hydrolyzable group include an alkoxy group (preferably having 1 to 10 carbon atoms) and a halogen atom such as a chlorine atom. The number of hydrolyzable groups directly bonded to Si atoms in the silane coupling agent is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit is preferably 10,000. The silane coupling agent also preferably has a reactive group. Examples of the reactive group include an epoxy group, an oxetanyl group, a vinyl group, a (meth)acrylic group, a styryl group, an amino group, an isocyanate group, a mercapto group, and an acid anhydride group. The number of reactive groups possessed by the silane coupling agent is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit is preferably 10,000 or less. Examples of silane coupling agents include 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0168] When the composition of the present invention contains a surface modifier, the surface-modified specific inorganic substance may be prepared in advance and used as part of the raw materials of the composition. That is, the surface-modified specific inorganic substance prepared in advance may be mixed with the other components of the composition, thereby introducing all or part of the surface modifier and the specific inorganic substance into the composition in a form contained in the surface-modified specific inorganic substance prepared in advance. Alternatively, a surface modifier and / or specific inorganic substance other than the surface modifier and specific inorganic substance introduced in the form contained in the surface-modified specific inorganic substance, but not forming a surface-modified specific inorganic substance, may be mixed with other components of the composition to introduce all or part of the surface modifier and / or specific inorganic substance into the composition. In this case, it is also preferable that the surface modifier is adsorbed onto the surface of the specific inorganic substance during the mixing process, forming the surface-modified specific inorganic substance in the composition. In this case, a portion of the surface modifier may be present in the composition in a state that does not contribute to the formation of the surface-modified specific inorganic substance. Although the above describes the specific inorganic substance, the specific inorganic substance may be replaced with other inorganic substances. In other words, the other inorganic substances may be surface-modified in the above manner.

[0169] The surface modifier may be used alone or in combination of two or more. The content of the surface modifier is preferably from 0.005 to 5 mass %, more preferably from 0.05 to 3 mass %, based on the total solid content of the composition. The content of the surface modifier is preferably 0.01 to 10 mass %, more preferably 0.10 to 5 mass %, based on the total mass of all inorganic substances, where "total inorganic substances" refers to the total content of the above-mentioned specific inorganic substances and other inorganic substances. The mass ratio of the mass of the surface modifier to the mass of the specific inorganic substance (mass of the surface modifier adsorbed on the surface of the specific inorganic substance / mass of the specific inorganic substance) is preferably 0.00001 to 0.5, more preferably 0.0001 to 0.1. The content of the surface-modified specific inorganic substance is preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 75% by mass or more, based on the total solid content of the composition. The upper limit is preferably less than 100% by mass, more preferably 95% by mass or less, and even more preferably 85% by mass or less.

[0170] [Acid anhydride] The composition may include an acid anhydride. An acid anhydride is a compound having one or more acid anhydride groups (groups represented by -CO-O-CO-).

[0171] The number of acid anhydride groups in the acid anhydride is 1 or more, preferably 2 or more, and more preferably 3 or more. The upper limit of the number is, for example, 1,000 or less. The molecular weight of the acid anhydride (weight average molecular weight when there is a molecular weight distribution) is preferably 100 or more, more preferably 2000 or more, and even more preferably 6000 or more. The upper limit of the molecular weight is preferably 100000 or less, more preferably 30000 or less, and even more preferably 17000 or less. The acid anhydride may be a low molecular weight compound or a high molecular weight compound. Examples of acid anhydrides that are low molecular weight compounds include maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. In the acid anhydride polymer compound, the acid anhydride group may be incorporated into the main chain or may be present in a side chain. For example, when the polymer compound has a repeating unit based on maleic acid, the acid anhydride group contained in the repeating unit is considered to be incorporated into the main chain.

[0172] The acid anhydride group may or may not form a ring together with atoms other than the atoms contained in the acid anhydride group. Among these, the acid anhydride group preferably forms a ring. The ring may be a monocyclic or polycyclic ring, and the number of ring atoms may be, for example, 5 to 15. For example, the acid anhydride preferably has a group represented by formula (A).

[0173] [ka]

[0174] In formula (A), * S and* T represents the bonding position to the carbon atom. however,* S and the carbon atom bonded with * T Carbon atoms bonded by are adjacent atoms that are directly bonded to each other. That is, a group represented by formula (A) and * Sand the carbon atom bonded with * T The carbon atoms bonded to it together form a five-membered ring. Also,* S and the carbon atom bonded with * T There is no limitation on the type of bond to the carbon atom bonded by the formula (A), and it may be, for example, a single bond or a double bond. S and the carbon atom bonded with * T The five-membered ring formed by the carbon atom bonded to the carbon atom is condensed to an aromatic ring (such as a benzene ring), and S and the carbon atom bonded with * T and the carbon atoms bonded to each other by may be adjacent ring atoms in the same aromatic ring. The aromatic ring may be monocyclic or polycyclic, may or may not contain heteroatoms, and may have 5 to 15 ring atoms, for example.

[0175] The acid anhydride preferably has a group selected from the group consisting of a group represented by formula (B), a group represented by formula (C), and a group represented by formula (D).

[0176] [ka]

[0177] In formula (B), R A1 ~R A4 Among these, one or two represent a bonding position, and the others each independently represent a hydrogen atom or a substituent. R A1 ~R A4 When two of the groups are bonding positions, for example, R A1 and R A2 may be the bonding site, and R A1 and R A2 Either one of the two and R A3 and R A4 and either one of the above may be the binding site. R A1 ~R A4Examples of the substituent that can be represented by the formula include groups selected from the above-mentioned substituent group Y. The total number of atoms other than hydrogen atoms in the above-mentioned substituent is, for example, 1 to 20.

[0178] In formula (C), R B1 and R B2 each independently represents a hydrogen atom, a substituent, or a bonding position. B1 and R B2 One or both of the following are binding sites: R B1 and R B2 Examples of the substituent that can be represented by the formula include groups selected from the above-mentioned substituent group Y. The total number of atoms other than hydrogen atoms in the above-mentioned substituent is, for example, 1 to 20.

[0179] In formula (D), * represents a bonding position, which may be a bonding position to a hydrogen atom. In formula (D), m represents 1 or 2. In formula (D), Ar represents an aromatic ring which may have a substituent. The aromatic ring may be monocyclic or polycyclic, may or may not have a heteroatom, and has, for example, 5 to 15 member atoms. Among these, the aromatic ring is preferably a benzene ring. In formula (D), n represents an integer of 0 or more, preferably an integer of 0 to 2, and more preferably 0 or 1. In formula (D), there are (n+1) five-membered rings each having a group represented by —CO—O—CO—, and the (n+1) five-membered rings are condensed with an aromatic ring represented by Ar. For example, when n is 0, the group represented by formula (D) is a group represented by the following formula (D0), and when n is 1, the group represented by formula (D) is a group represented by the following formula (D1). *, m, and Ar in the following formula (D0) and formula (D1) are the same as *, m, and Ar in formula (D), respectively.

[0180] [ka]

[0181] The number of groups represented by formula (A) that the acid anhydride has is preferably 1 or more, more preferably 2 or more. The upper limit of the number is, for example, 1,000 or less. The number of groups selected from the group consisting of the group represented by formula (B) and the group represented by formula (C) contained in the acid anhydride is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit of the number is, for example, 1,000 or less. The number of groups represented by formula (D) in the acid anhydride is preferably at least 1. The upper limit of the number is, for example, 1,000 or less.

[0182] Among these, the acid anhydride is preferably a polymer compound. The acid anhydride preferably has a repeating unit represented by the following formula (X), and more preferably has a repeating unit represented by formula (X) and a repeating unit represented by formula (Y).

[0183] [ka]

[0184] In formula (Y), R Y represents an aromatic ring group which may have a substituent. The aromatic ring group may be monocyclic or polycyclic, and may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of heteroatoms in the aromatic heterocyclic group include oxygen, sulfur, and nitrogen atoms. The aromatic ring group preferably has 5 to 15 ring atoms. Examples of the substituent that the aromatic ring group may have include groups selected from the above-mentioned substituent group Y. The total number of atoms other than hydrogen atoms in the substituent is, for example, 1 to 20. The aromatic ring group may have 0 to 5 substituents, for example. Among them, R Y is preferably an unsubstituted benzene ring group. The repeating unit represented by formula (Y) may be used alone or in combination of two or more.

[0185] When the acid anhydride has a repeating unit represented by formula (X), the content thereof is preferably 1 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass %, based on all repeating units of the acid anhydride. When the acid anhydride has a repeating unit represented by formula (Y), the content thereof is preferably 10 to 90 mass % based on the total repeating units of the acid anhydride.

[0186] The acid anhydride may have a repeating unit other than the repeating unit represented by formula (X) or formula (Y), and may have, for example, a repeating unit represented by the following formula (Z).

[0187] [ka]

[0188] In formula (Z), R Z1 ~R Z4 R each independently represents a hydrogen atom or a substituent. Z1 ~R Z4 It is also preferred that 0 to 2 of these be the above-mentioned substituents. Examples of the substituent include groups selected from the above-mentioned substituent group Y. The total number of atoms other than hydrogen atoms in the substituent is, for example, 1 to 20. Among these, the above-mentioned substituents are each independently preferably -COOH, -O-CO-R, or a linear or branched alkyl group. R in -O-CO-R represents an organic group, preferably a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the repeating unit represented by formula (Z) include R Z1 ~R Z4 are all hydrogen atoms, R Z1 and R Z3 is a hydrogen atom and R Z2 and RZ4 A repeating unit in which R is -COOH, and Z1 ~R Z3 is a hydrogen atom and R Z4 is -O-CO-R. However, the repeating unit represented by formula (Z) is a repeating unit different from the repeating unit represented by formula (Y). Z1 ~R Z4 A repeating unit represented by formula (Z) does not include a repeating unit in which three of the groups are hydrogen atoms and one is an aromatic ring group. The repeating unit represented by formula (Z) may be used alone or in combination of two or more. When the acid anhydride has a repeating unit represented by formula (Z), the content thereof is preferably 1 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass %, based on all repeating units of the acid anhydride.

[0189] Commercially available acid anhydrides may be used, such as the SMA series manufactured by Tomoe Engineering Co., Ltd. (the XIRAN series manufactured by Polyscope Polymers BV), the OREVAC T series manufactured by Arkema, and the Arastar series manufactured by Arakawa Chemical Industries, Ltd.

[0190] Only one type of acid anhydride may be used, or two or more types may be used. The content of the acid anhydride is preferably from 0.01 to 40% by mass, more preferably from 0.1 to 10% by mass, and even more preferably from 0.6 to 5% by mass, based on the total solid content of the composition. The content of the acid anhydride is preferably from 0.1 to 100% by mass, more preferably from 1 to 70% by mass, and even more preferably from 5 to 60% by mass, based on the total content of the epoxy compound and the phenol compound.

[0191] [Maleimide Compound] The composition of the present invention preferably further contains a maleimide compound, since the heat resistance (glass transition temperature Tg) of the thermally conductive material is excellent. When the composition contains a maleimide compound, it is believed that the maleimide compound undergoes an addition reaction with the phenol compound, and / or the polymer structure produced by the addition reaction forms an interpenetrating network structure with the polymer structure formed by the other components in the composition, thereby further improving the density of the polymer structure of the thermal conductive material and further increasing the thermal conductivity and heat resistance (Tg) of the thermal conductive material. Furthermore, the formation of a denser polymer structure within the thermal conductive material makes it difficult for water to penetrate the material, reducing its hygroscopicity. Furthermore, when the thermal conductive material is exposed to high temperatures, the thermal decomposition of its components and the generation of volatile small molecules within the material are also reduced. As a result, even when the thermal conductive material is exposed to high temperatures, the evaporation of volatile components from the thermal conductive material and the resulting loss of adhesiveness are prevented, which is thought to further improve the solder heat resistance of the thermal conductive material.

[0192] The maleimide compound means a maleimide compound having one or more maleimide groups. Among these, the maleimide compound is preferably a maleimide compound having one or two maleimide groups, and more preferably a maleimide compound having two maleimide groups (bismaleimide compound).

[0193] The number of maleimide groups that the maleimide compound has is 1 or more, preferably 1 to 100, more preferably 2 to 10, and even more preferably 2. The maleimide compound may be either a high molecular weight compound or a low molecular weight compound. The molecular weight of the maleimide compound is preferably 100 to 3,000, more preferably 200 to 2,000, and even more preferably 300 to 1,000.

[0194] The maleimide group contained in the maleimide compound is preferably a group represented by formula (M).

[0195] [ka]

[0196] In formula (M), * represents a bonding position, and X and Y each independently represent a hydrogen atom or a substituent.

[0197] X and Y each independently represent a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified in the group Y of substituents described above. X and Y are preferably hydrogen atoms.

[0198] The maleimide compound is also preferably a compound having one or more (preferably 1 to 10) aromatic ring groups (such as benzene ring groups). The maleimide compound is preferably a compound represented by the following formula (1):

[0199] [ka]

[0200] In formula (1), m represents 0 or 1. m is preferably 1. n represents 0 or 1. n is preferably 1.

[0201] In formula (1), R 1 and R 2 each independently represents a hydrogen atom or a substituent. The substituent is preferably an alkyl group. The alkyl group may be linear or branched, and preferably has 1 to 10 carbon atoms. R 1 and / or R 2 When represents a substituent, R 1 and / or R 2 is also preferably located adjacent to the maleimide group on the benzene ring group. R 1 and R 2 If both represent substituents, R 1 and R 2 are preferably different substituents, and R 1 represents a methyl group, and R 2More preferably, represents an ethyl group.

[0202] In formula (1), L 1 represents a divalent linking group. Examples of the divalent linking group include an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S-), -SO2-, -NR- (R is a hydrogen atom or an alkyl group), a divalent aliphatic hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group (-CH=CH-, etc.), and an alkynylene group (-C≡C-, etc.)), a divalent aromatic ring group (an arylene group and a heteroarylene group), and a group formed by combining these. In formula (1), L 1 The divalent linking group represented by the following formula preferably has 1 or more carbon atoms, more preferably 1 to 100 carbon atoms, and even more preferably 3 to 15 carbon atoms.

[0203] Among them, L 1 teeth,"* p -(L 2 -Ar) k -* q " is preferred. * q represents the bonding position on the side directly bonding to the maleimide group, and * p represents the opposite binding position. k represents an integer of 1 or more, preferably 1 to 10, and more preferably 1. L 2 is a single bond, -C(R 3 )(R 4 )-, -O- or -CO-, -C(R 3 )(R 4 )- is preferred. R 3 and R 4 each independently represents a hydrogen atom or a substituent, and is preferably an alkyl group (which may be linear or branched and has 1 to 10 carbon atoms). Ar represents an arylene group. The number of ring atoms in the arylene group is preferably 6 to 15, more preferably 6. When the arylene group has a substituent, the number of the substituent is preferably 1 to 4, more preferably 1 to 2. The substituent that the arylene group may have is preferably an alkyl group (which may be linear or branched, and has 1 to 10 carbon atoms). Examples of structures that Ar can have include R 1 and R 2 and a structure that can be a benzene ring group bonded to the L 2 and when there are multiple Ar, there are multiple L 2 The Ar groups and the Ar groups present in plural may be the same or different.

[0204] If n is 1, R 1 and R 2 On the benzene ring group bonded to the maleimide group, 1 ) m The two groups represented by the "-maleimide group" may be positioned at the ortho position, the meta position, or the para position relative to each other. Of these, it is preferable that the two groups are positioned at the meta position or the para position.

[0205] Among them, the compound represented by formula (1) is a compound represented by formula (1) in which m represents 1, n represents 1, and L 1 The divalent linking group represented by the following formula preferably has 3 to 15 carbon atoms.

[0206] The maleimide compound may be used alone or in combination of two or more kinds. The content of the maleimide compound is preferably from 0.1 to 40 mass %, more preferably from 1 to 15 mass %, and even more preferably from 3.5 to 8 mass %, based on the total solid content of the composition. The content of the maleimide compound is preferably 1 to 200 mass %, more preferably 5 to 100 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total content of the epoxy compound and the phenol compound. The content of the maleimide compound is preferably from 1 to 500% by mass, more preferably from 20 to 300% by mass, still more preferably from 50 to 200% by mass, and particularly preferably from 70 to 130% by mass, based on the content of the phenol compound.

[0207] [Curing accelerator] The composition preferably further comprises a curing accelerator. Examples of the curing accelerator include onium salt-based curing accelerators such as tris-orthotolylphosphine, triphenylphosphine, boron trifluoride amine complex, the compounds described in paragraph

[0052] of JP-A-2012-067225, tetraphenylphosphonium tetraphenylborate (TPP-K), tetraphenylphosphonium tetra-p-tolylborate (TPP-MK), tetra-n-butylphosphonium laurate (TBP-LA), bis(tetra-n-butylphosphonium)pyromellitate, and tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenylsilicate adducts, and other quaternary phosphonium compounds (phosphonium salts). Examples of the curing accelerator include 2-methylimidazole (trade name: 2MZ), 2-undecylimidazole (trade name: C11-Z), 2-heptadecylimidazole (trade name: C17Z), 1,2-dimethylimidazole (trade name: 1.2DMZ), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), 2-phenylimidazole (trade name: 2PZ), 2-phenyl-4-methylimidazole (trade name: 2P4MZ), and 1-benzyl-2-methylimidazole (trade name: 1B 2MZ), 1-benzyl-2-phenylimidazole (trade name: 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name: 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZ-A), 2,4-diamino-6-[2'-undecylimidazole]-methyl-s-triazine (trade name: 2MZ-CNS ... Cilimidazolyl-(1')]-ethyl-s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2-phenyl-4-methyl-5- Examples of imidazole-based curing accelerators include hydroxymethylimidazole (trade name: 2P4MHZ-PW), 1-cyanoethyl-2-phenylimidazole (trade name: 2PZ-CN), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZA-PW), and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (trade name: 2MAOK-PW) (all manufactured by Shikoku Chemical Industry Co., Ltd.). Furthermore, examples of triarylphosphine-based curing accelerators include the compounds described in paragraph

[0052] of JP 2004-043405 A.Examples of phosphorus-based curing accelerators in which triphenylborane is added to triarylphosphine include the compounds described in paragraph

[0024] of JP-A-2014-005382.

[0208] Among these, the curing accelerator preferably contains a compound having a phosphorus atom or a phosphonium salt, and more preferably contains a compound having a phosphorus atom. The curing accelerator may be a compound having a phosphorus atom or a phosphonium salt itself. When a phosphonium salt is used as the curing accelerator, the storage stability of the semi-cured film formed from the composition is excellent.

[0209] The curing accelerator may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.002% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.07% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the composition. The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and even more preferably 0.55% by mass or more, based on the total amount of epoxy compounds. The upper limit is preferably 40% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of epoxy compounds. The content of the compound having a phosphorus atom or the phosphonium salt is preferably from 10 to 100 mass %, more preferably from 50 to 100 mass %, and even more preferably from 80 to 100 mass %, based on the total mass of the curing accelerator.

[0210] [Ion scavenger] The composition of the present invention preferably further contains an ion scavenger, in order to provide excellent insulating properties to the thermally conductive material. The ion scavenger adsorbs ionic impurities in the composition or in a thermally conductive material formed using the composition. Examples of the ion scavenger include inorganic ion scavenger and organic ion scavenger. All or part of the above-mentioned specific inorganic substances and other inorganic substances may also function as ion scavengers.

[0211] Examples of inorganic ion trapping agents include inorganic ion adsorbents such as cation adsorbents that trap cations by ion exchange, anion adsorbents that trap anions by ion exchange, and amphoteric ion trapping agents that trap both cations and anions by ion exchange.

[0212] Examples of inorganic ion scavengers include inorganic substances (preferably composite inorganic substances) containing one or more (preferably two or more) selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, and magnesium. Examples of inorganic substances (preferably composite inorganic substances) containing one or more (preferably two or more) of the above-mentioned elements include oxides (preferably composite oxides), oxide hydrates (preferably composite oxide hydrates), and hydroxides (preferably composite hydroxides). Further, examples of inorganic ion scavengers include composite inorganic materials (composite oxides, complex oxide hydrates, complex hydroxides, etc.) of aluminum with one or more elements selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, and magnesium. An example of the composite oxide is an aluminum oxide / magnesium oxide solid solution.

[0213] The composite inorganic ion scavenger is preferably an oxide (composite oxide), oxide hydrate (composite oxide hydrate), or hydroxide (composite hydroxide) of two or more types selected from the group consisting of antimony, bismuth, zirconium, magnesium, and aluminum. Among these, preferred inorganic ion scavengers are ternary composites of magnesium, aluminum, and zirconium (composite oxides, composite oxide hydrates, composite hydroxides, etc.), binary composites of bismuth and zirconium (composite oxides, composite oxide hydrates, composite hydroxides, etc.), binary composites of bismuth and antimony (composite oxides, composite oxide hydrates, composite hydroxides, etc.), or composites containing magnesium and aluminum (composite oxides, composite oxide hydrates, composite hydroxides, etc.), with binary composites of bismuth and zirconium and binary composites of magnesium and aluminum being more preferred.

[0214] When the inorganic ion scavenger contains two or more types of metal atoms, the content of the inorganic ion scavenger preferably contains two or more types (e.g., two to four types) of metal atoms that account for 1 to 99 mol % of the total metal atoms in the inorganic ion scavenger, and more preferably contains two or more types (e.g., two to four types) of metal atoms that account for 5 to 95 mol % of the total metal atoms in the inorganic ion scavenger. The content of the inorganic ion scavenger is preferably 0.01 to 40 mass %, more preferably 0.1 to 20 mass %, and even more preferably 0.2 to 10 mass %, based on the total amount of inorganic substances.

[0215] Examples of organic ion scavengers include triazine thiol compounds, triazine amine compounds, benzimidazole compounds, benzotriazole compounds, aminotriazole compounds, and bisphenol reducing agents.

[0216] An example of the triazine thiol compound is 2-dibutylamino-4,6-dimercapto-s-triazine. The benzimidazole compound includes, for example, benzimidazole. Examples of benzotriazole compounds include 1H-benzotriazole, carboxybenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol]. Examples of aminotriazole compounds include 3-amino-1,2,4-triazole and 3,5-diamino-1,2,4-triazole. Examples of bisphenol reducing agents include 2,2'-methylenebis-(4-ethyl-6-t-butylphenol) and 4,4'-butylidenebis-(6-t-butyl-3-methylphenol).

[0217] The ion trapping agent may be a commercially available ion trapping agent. Examples of commercially available ion scavengers include DHF-4A, DHT-4A, DHT-4A-2, DHT-4C, Kyoward 500, KW-2000, and KW-2100 (trade names, manufactured by Kyowa Chemical Industry Co., Ltd.); IXE-100, IXE-500, IXE-600, IXE-700F, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS-A2, and IXEPLAS-B1 (trade names, manufactured by Toagosei Co., Ltd.); Jisnet DB (trade name, manufactured by Sankyo Pharmaceutical Co., Ltd.); VD-3 and VD-5 (trade names, manufactured by Shikoku Chemical Industry Co., Ltd.); and Yoshinox BB (trade name, manufactured by Yoshitomi Pharmaceutical Co., Ltd.).

[0218] The ion scavenger may be used alone or in combination of two or more. When the composition contains an ion scavenger, the content of the ion scavenger (inorganic ion scavenger and / or organic ion scavenger) is preferably 0.01 to 10 mass%, more preferably 0.1 to 20 mass%, and even more preferably 0.2 to 10 mass%, based on the total solid content of the composition. When the ion scavenger contains an inorganic ion scavenger, part or all of the ion scavenger may simultaneously fall under the category of the above-mentioned specific inorganic substance or other inorganic substance.

[0219] 〔solvent〕 The composition may include a solvent. The solvent is preferably an organic solvent, such as cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane, and tetrahydrofuran. When the composition contains a solvent, the content of the solvent is preferably an amount that makes the solids concentration of the composition 20 to 90 mass %, more preferably an amount that makes 30 to 85 mass %, and even more preferably an amount that makes 50 to 80 mass %. The content of the solvent is preferably from 10 to 80% by mass, more preferably from 15 to 70% by mass, and even more preferably from 20 to 50% by mass, based on the total mass of the composition.

[0220] [Method for producing the composition] The method for producing the composition is not particularly limited, and any known method can be used, for example, by mixing the various components described above. When mixing, the various components may be mixed all at once or sequentially. The method for mixing the components is not particularly limited, and known methods can be used. The mixing device used for mixing is preferably a submerged disperser, and examples include agitators such as planetary centrifugal mixers and high-speed rotary shear agitators, colloid mills, roll mills, high-pressure injection dispersers, ultrasonic dispersers, bead mills, and homogenizers. One type of mixing device may be used alone, or two or more types may be used in combination. Degassing treatment may be performed before, after, and / or simultaneously with mixing.

[0221] [Method of curing the composition] The composition of the present invention is preferably a composition for forming a thermally conductive material. The composition of the present invention is cured to obtain a thermally conductive material. The method for curing the composition is not particularly limited, but a thermal curing reaction is preferred. The heating temperature during the thermosetting reaction is not particularly limited and may be appropriately selected within the range of, for example, 50 to 250° C. Furthermore, when carrying out the thermosetting reaction, heat treatments at different temperatures may be carried out multiple times. The curing treatment is preferably carried out on a composition in the form of a film or sheet. Specifically, for example, the composition may be applied to form a film and then subjected to a curing reaction. When performing the curing treatment, it is preferable to apply the composition to a substrate to form a coating film and then cure it. In this case, the coating film formed on the substrate may be brought into contact with another substrate before the curing treatment. The cured product (thermal conductive material) obtained after curing may or may not be separated from one or both of the substrates. Alternatively, when carrying out the curing treatment, the composition may be applied to separate substrates to form coating films on each substrate, and the curing treatment may be carried out while the resulting coating films are in contact with each other. The cured product (thermal conductive material) obtained after curing may or may not be separated from one or both of the substrates.

[0222] The curing treatment may be completed when the composition is in a semi-cured state, or after the composition is in a semi-cured state, further curing treatment may be carried out to complete the curing. The curing treatment for bringing the composition into a semi-cured state (hereinafter also referred to as "semi-curing treatment") and the curing treatment for complete curing (hereinafter also referred to as "main curing treatment") may be carried out in separate steps.

[0223] In the semi-curing treatment, for example, a composition is applied to a substrate to form a coating film, and then the coating film on the substrate may be heated without pressure to form a semi-cured thermal conductive material (also referred to as a "semi-cured film" or "semi-cured sheet"). Alternatively, the coating film on the substrate may be heated while also being pressed to form a semi-cured film. When press processing is performed, the press processing may be performed before, after, or during the heating process. Press processing in the semi-curing treatment may facilitate adjustment of the film thickness of the resulting semi-cured film and / or reduction of the amount of voids in the semi-cured film. The semi-curing treatment may be carried out in a state where coating films formed on different substrates are laminated together, or may be carried out without laminating the coating films together. The semi-curing treatment may also be carried out in a state where the coating film formed from the composition is in contact with a material other than the coating film.

[0224] The resulting semi-cured film may be used as a heat conductive material as is, or may be further subjected to a main curing treatment and then used as a completely cured heat conductive material. In the main curing treatment, the semi-cured film may be heated as is without pressure, or may be heated after or while being pressed. In this case, the main curing treatment may be performed in a state where separate semi-cured films are stacked on top of each other, or may be performed without stacking the semi-cured films on top of each other. The main curing treatment may be carried out in a state where the semi-cured film is placed in contact with a device or the like in which it is used. It is also preferable that the main curing treatment adheres the device to the thermally conductive material of the present invention.

[0225] There are no limitations on the press used for press working that may be carried out during the hardening treatment in the semi-hardening treatment and / or the full hardening treatment, and for example, a flat press or a roll press may be used. When using a roll press, for example, it is preferable to sandwich a coated substrate obtained by forming a coating film on a substrate between a pair of opposing rolls, and apply pressure in the film thickness direction of the coated substrate while rotating the pair of rolls to pass the coated substrate. The coated substrate may have a substrate on only one side of the coating film, or may have a substrate on both sides of the coating film. The coated substrate may be passed through the roll press once or multiple times. During the hardening treatment in the semi-hardening treatment and / or the full hardening treatment, either one of the treatment by platen pressing and the treatment by roll pressing may be carried out, or both may be carried out.

[0226] For information on the production of thermally conductive materials, including curing reactions, please also refer to "High Thermal Conductivity Composite Materials" (CMC Publishing, written by Takezawa Yoshitaka).

[0227] The thermally conductive material can be formed into various shapes depending on the application. A typical shape of the formed thermally conductive material is, for example, a sheet shape. That is, the thermally conductive material obtained using the composition of the present invention is preferably a thermally conductive sheet. Furthermore, it is preferable that the thermal conductivity of the thermally conductive material obtained using the composition of the present invention is isotropic rather than anisotropic.

[0228] The thermally conductive material is preferably insulating (electrically insulating), in other words, the composition of the present invention is preferably a thermally conductive insulating composition. The volume resistivity of the thermal conductive material at 23°C and 65% relative humidity is 10 10 Ω·cm or more is preferable, and 10 12 Ω·cm or more is preferable, and 10 14 More preferably, the resistivity is 10 Ω·cm or more. 18 Ω·cm or less is preferable.

[0229] [Uses of thermal conductive materials] The thermally conductive material obtained using the composition of the present invention can be used as a heat dissipation material such as a heat dissipation sheet, and can be used for heat dissipation applications in various devices. More specifically, a device with a thermally conductive layer can be produced by disposing a thermally conductive layer containing the thermally conductive material of the present invention (or a thermally conductive layer containing a thermally conductive sheet) on the device, and the heat generated from the device can be efficiently dissipated by the thermally conductive layer. The thermally conductive layer may be a thermally conductive layer containing a thermally conductive multilayer sheet, which will be described later. The thermally conductive material obtained using the composition of the present invention has sufficient thermal conductivity and high heat resistance, and is therefore suitable for heat dissipation applications in power semiconductor devices used in electrical equipment such as personal computers, general home appliances, and automobiles. Furthermore, since the thermally conductive material obtained using the composition of the present invention has sufficient thermal conductivity even in a semi-cured state, it can be used as a heat dissipation material to be placed in areas where it is difficult for light for photocuring to reach, such as gaps between components of various devices.In addition, since it has excellent adhesive properties, it can also be used as a thermally conductive adhesive.

[0230] The thermally conductive material obtained using the composition of the present invention may be used in combination with other components other than the component formed from the present composition. For example, a thermally conductive material (such as a thermally conductive sheet) may be combined with a support (adherend) other than the layer formed from the present composition. Examples of the support (adherend) include plastic materials, metal materials, and glass. Examples of the plastic materials include polyesters such as polyethylene terephthalate (PET), polycarbonate, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, and silicones. Examples of the metal materials include copper and aluminum. The support (adherend) is also preferably in the form of a sheet. The thickness of the sheet-like thermally conductive material (thermally conductive sheet) is preferably 100 to 300 μm, more preferably 150 to 250 μm.

[0231] Furthermore, an adhesive layer and / or a pressure-sensitive adhesive layer may be combined with the thermally conductive material (preferably a thermally conductive sheet). By joining the thermally conductive material to an object to which heat should be transferred, such as a device, via the adhesive layer and / or pressure-sensitive adhesive layer, a stronger bond between the thermally conductive material and the object can be achieved. The thermally conductive material formed from the composition of the present invention also has good adhesion to the adhesive layer and pressure-sensitive adhesive layer, and peeling at the interface between the thermally conductive material and the adhesive layer or pressure-sensitive adhesive layer can be suppressed. For example, a thermally conductive multilayer sheet may be produced which has a thermally conductive sheet and an adhesive layer or pressure-sensitive adhesive layer provided on one or both sides of the thermally conductive sheet. One or both sides of the thermally conductive sheet may be provided with either an adhesive layer or a pressure-sensitive adhesive layer, or both. An adhesive layer may be provided on one side of the thermally conductive sheet, and a pressure-sensitive adhesive layer may be provided on the other side. Furthermore, an adhesive layer and / or a pressure-sensitive adhesive layer may be provided partially or entirely on one or both sides of the thermally conductive sheet. As described above, in the present invention, the thermally conductive material such as the thermally conductive sheet may be in a semi-cured state (semi-cured film), and the thermally conductive sheet in the thermally conductive multilayer sheet may be in a semi-cured state. The adhesive layer in the thermally conductive multilayer sheet may be in a cured, semi-cured, or uncured state. [Example]

[0232] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0233] [Preparation and Evaluation of Compositions] [Various ingredients] The various components used in the examples and comparative examples are listed below.

[0234] <Phenol compounds>

[0235] [ka]

[0236] <Epoxy compounds> The weight average molecular weight of B-8 was 3,000, and the average value of n of B-9 was 10.

[0237] [ka]

[0238] <Curing accelerator> C-1: Tris(orthotolyl)phosphine C-2: Triphenylphosphine C-3: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) C-4: TPP-MK (tetraphenylphosphonium tetra-p-tolylborate)

[0239] <Specific inorganic substances or surface-modified specific inorganic substances> The specific inorganic substances or surface-modified specific inorganic substances used in each Example and Comparative Example are shown below. Note that in all surface-modified specific inorganic substances, the content of the surface modifier was more than 0 mass % and less than 1 mass % relative to the total mass of the surface-modified specific inorganic substance.

[0240] <Agglomerated boron nitride> HP-40: Agglomerated boron nitride (HP-40 MF100, average particle size: 40 μm, manufactured by Mizushima Ferroalloy Co., Ltd.) BN-A: Surface-modified agglomerated boron nitride produced by Production Method A shown below BN-B: Surface-modified agglomerated boron nitride produced by Production Method B shown below BN-C: Surface-modified agglomerated boron nitride produced by Production Method C shown below BN-D: Surface-modified agglomerated boron nitride produced by production method D shown below BN-E: Surface-modified agglomerated boron nitride produced by Production Method E shown below

[0241] (Manufacturing method A) Agglomerated boron nitride (HP-40 MF100) (15 g) was subjected to vacuum plasma treatment (gas type: O2, pressure: 30 Pa, output: 500 W) using a Plasma Cleaner PDC210 (Yamato Scientific Co., Ltd.). The agglomerated boron nitride to be treated was stirred every 5 minutes of vacuum plasma treatment, and vacuum plasma treatment was continued until the total treatment time reached 30 minutes, yielding modified boron nitride particles A. The obtained modified boron nitride particles A were stirred in acetonitrile (30 ml), and a hydrolysis adjusted solution (0.42 g) of a silane coupling agent (X12-984S, manufactured by Shin-Etsu Chemical Co., Ltd.) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours to carry out an adsorption treatment. The modified boron nitride particles A in the acetonitrile were filtered, washed with acetonitrile (30 ml), and dried in an oven at 40°C to obtain BN-A. The hydrolysis-adjusted solution of the silane coupling agent was prepared by mixing silane coupling agent (1 g), ethanol (500 μL), 2-propanol (500 μL), water (720 μL) and acetic acid (100 μL) and stirring for 1 hour. In the following examples and comparative examples, the composition of the hydrolysis-adjusted solution of the silane coupling agent is the same unless otherwise specified. "X12-984S" is a polymer-type silane coupling agent having an epoxy group and an ethoxysilyl group.

[0242] (Manufacturing method B) Agglomerated boron nitride (HP-40 MF-100, 50 g) was added to an aqueous NaOH solution (40 g NaOH / 400 ml water) and stirred. After adding aqueous sodium persulfate (9.6 g sodium persulfate / 100 ml water) to the NaOH solution, the temperature of the NaOH solution was raised to 50°C and the solution was stirred for an additional 3 hours. A Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) was used for stirring at a rotation speed of 150 rpm. After cooling the NaOH solution to room temperature, the aggregated boron nitride particles B in the NaOH solution were filtered out and washed with water (500 ml) and acetonitrile (250 ml) to obtain modified boron nitride particles B. The resulting modified boron nitride particles B were stirred in acetonitrile (100 ml), and a hydrolysis adjustment solution (1.25 g) of a silane coupling agent (X12-984S, manufactured by Shin-Etsu Chemical Co., Ltd.) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours to perform an adsorption treatment. The modified boron nitride particles B in the acetonitrile were filtered, washed with acetonitrile (100 ml), and dried in an oven at 40°C to obtain BN-B.

[0243] (Manufacturing method C) Boron nitride (HP-40 MF-100, 50 g) was added to water (400 ml) and stirred to obtain a mixed solution. Sodium hypochlorite water (sodium hypochlorite pentahydrate: 48 g / water: 100 ml) was further added to the mixed solution, and the mixed solution was then heated to 50°C and stirred for an additional 3 hours. A Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) was used for stirring at 150 rpm. After the mixture was cooled to room temperature, the agglomerated boron nitride particles in the mixture were filtered out and washed with water (500 ml) and acetonitrile (250 ml) to obtain modified boron nitride particles C. The resulting modified boron nitride particles C were stirred in acetonitrile (100 ml), and a hydrolysis adjustment solution (1.25 g) of a silane coupling agent (X12-984S) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours to perform an adsorption treatment. The modified boron nitride particles C in the acetonitrile were filtered, washed with acetonitrile (100 ml), and dried in an oven at 40°C to obtain BN-C.

[0244] (Manufacturing method D) Agglomerated boron nitride (HP-40 MF-100, 50 g) was heated at 1000°C for 1 hour to obtain modified boron nitride particles D. The obtained modified boron nitride D was reslurried and washed with water (500 ml), filtered, and then stirred in acetonitrile (100 ml). A hydrolysis adjustment solution (1.25 g) of a silane coupling agent (KBM-403) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours to perform an adsorption treatment. The modified boron nitride particles D in the acetonitrile were filtered, washed with acetonitrile (100 ml), and dried in an oven at 40°C to obtain BN-D.

[0245] (Manufacturing method E) Modified boron nitride particles E were obtained by heating aggregated boron nitride (HP-40 MF-100, 50 g) at 900°C for 4 hours. The obtained modified boron nitride E was reslurried and washed with water (500 ml), filtered, and then stirred in acetonitrile (100 ml). A hydrolysis adjustment solution (1.25 g) of a silane coupling agent (KBM-403) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours to perform an adsorption treatment. The modified boron nitride particles E in the acetonitrile were filtered, washed with acetonitrile (100 ml), and dried in an oven at 40°C to obtain BN-E.

[0246] <Inorganic material X> AA-03F: Aluminum oxide (average particle size: 0.25 μm, manufactured by Sumitomo Chemical Co., Ltd.) Surface-modified AA-03F: Surface-modified aluminum oxide (average particle size: 0.25 μm, manufactured by Sumitomo Chemical Co., Ltd.) QSG-100: Surface-modified silicon dioxide (average particle size: 0.11 μm, manufactured by Shin-Etsu Silicone Co., Ltd.) QSG-10: Surface-modified silicon dioxide (average particle size: 0.015 μm, manufactured by Shin-Etsu Silicone Co., Ltd.)

[0247] <Inorganic Y> Surface-modified AA-3: Surface-modified aluminum oxide (average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd., also applicable to other surface-modified inorganic substances) AA-04: Aluminum oxide (average particle size: 0.40 μm, manufactured by Sumitomo Chemical Co., Ltd.)

[0248] <Maleimide compounds> F-1: Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (Fujifilm)

[0249] <Acid anhydride> H-1: Styrene-maleic anhydride copolymer (XIRAN EF-40, manufactured by Polyscope Polymers BV)

[0250] <Ion scavenger> G-1: KW-2000, Aluminum oxide / Magnesium oxide solid solution (Mg 0.7 Al 0.3 O 1.15 ) (Kyowa Chemical Industry Co., Ltd.) G-2: IXE-6107, Zr, Bi system (manufactured by Toagosei Co., Ltd.)

[0251] <Solvent> Cyclopentanone was used as the solvent.

[0252] [Preparation of Composition] A mixture was prepared by blending the epoxy compounds and phenol compounds in the combinations shown in Table 1 below in equivalent amounts (amounts in which the number of epoxy groups in the epoxy compound is equal to the number of hydroxyl groups in the phenol compound). The above mixture, solvent, optional ion scavenger, optional acid anhydride, optional maleimide compound, and curing accelerator were mixed in this order, and then the specific inorganic substance, surface-modified specific inorganic substance, or optional inorganic substance Y was added. The resulting mixture was treated for 5 minutes in a planetary centrifugal mixer (THINKY Corporation, Awatori Rentaro ARE-310) to obtain a composition (curable composition) of each Example or Comparative Example.

[0253] The amount of solvent added in each Example and Comparative Example was such that the solid content concentration of the composition in each Example and Comparative Example was 50 to 80 mass %. The solid content of each composition was adjusted within the above range so that the viscosity of each composition was approximately the same. The amounts of the epoxy compound and the phenol compound added were adjusted so that the total content of the epoxy compound and the phenol compound would be the amount shown in the "Total amount (mass%)" column in Table 1 relative to the total solid content of the composition, and so that the epoxy compound and the phenol compound would be equivalent amounts (amounts in which the number of epoxy groups in the epoxy compound is equal to the number of hydroxyl groups in the phenol compound).

[0254] [evaluation] [Preparation of semi-cured sheet (semi-cured film)] Using an applicator with a micrometer, the prepared composition was uniformly applied onto the release surface of a release-treated PET film (PET756501 manufactured by Lintec Corporation, film thickness 75 μm), and then dried at 120°C for 4 minutes to produce a semi-cured sheet (semi-cured film).

[0255] [Preparation of thermal conductive sheet (semi-cured film)] The resulting semi-cured sheet was covered with a release-treated PET film and heat-pressed in air (heat plate temperature 180°C, pressure 5 MPa, 5 minutes). This was then heat-treated at 180°C under normal pressure for 90 minutes to obtain a resin sheet. The PET films on both sides of the resin sheet were peeled off to obtain a thermally conductive sheet (thermal conductive material) with an average thickness of 120 μm.

[0256] [Evaluation of thermal conductivity] The thermal conductivity was evaluated using the thermally conductive sheet obtained in the above [Preparation of thermally conductive sheet (semi-cured film)]. (1) The thermal diffusivity of the thermal conductive sheet in the thickness direction was measured using the laser flash method using the NETZSCH LFA467. (2) Using a Mettler-Toledo balance "XS204," the specific gravity of the thermal conductive sheet was measured using the Archimedes method (using a "solid specific gravity measurement kit"). (3) Using a Seiko Instruments DSC320 / 6200, the specific heat of the thermally conductive sheet at 25°C was determined under a temperature increase condition of 10°C / min. (4) The thermal conductivity of the thermal conductive sheet was calculated by multiplying the obtained thermal diffusivity by the specific gravity and specific heat.

[0257] The thermal conductivity of the thermally conductive sheet was classified according to the following criteria, and the thermal conductivity of the thermally conductive sheet (thermally conductive material) obtained using the composition of each Example or Comparative Example was evaluated. A + :17W / mK or more A: 15W / mK or more and less than 17W / mK B: 13W / mK or more and less than 15W / mK C: 10W / mK or more and less than 13W / mK D: Less than 10W / mK

[0258] [Evaluation of heat resistance (Tg)] The Tg of the thermally conductive sheet obtained in the above [Preparation of thermally conductive sheet (semi-cured film)] was measured. The measurement was performed using a dynamic viscoelasticity measuring device "Rheogel-E4000" manufactured by UBM, and the tan δ peak at a frequency of 1 Hz was taken as Tg. The temperature was increased at a rate of 5°C / min in the range of 25 to 300°C.

[0259] The Tg of the thermally conductive sheet was classified according to the following criteria, and the heat resistance of the thermally conductive sheet (thermally conductive material) obtained using the composition of each Example or Comparative Example was evaluated. A: 170℃ or higher B: 160℃ or higher but lower than 170℃ C: Less than 160℃

[0260] [Evaluation of insulation properties] Using the thermally conductive sheet obtained in the above [Preparation of thermally conductive sheet (semi-cured film)], a voltage of 1 kV was applied in an environment of 85°C and 85% RH, and the time until the sample experienced dielectric breakdown was measured. The time until the sample experienced dielectric breakdown was classified according to the following criteria and used to evaluate the insulating properties of the thermally conductive sheets (thermally conductive materials) obtained using the compositions of each Example or Comparative Example. A: More than 500 hours B: 100 hours or more but less than 500 hours C: Less than 100 hours

[0261] [Evaluation of solder heat resistance] The semi-cured sheet obtained in the above "Preparation of semi-cured sheet (semi-cured film)" was sandwiched between a copper substrate having a thickness of 2 mm and copper foil having a thickness of 0.15 mm, and then heat-pressed in air (heat plate temperature 180°C, pressure 5 MPa, treatment for 5 minutes) to obtain a laminate having a "copper substrate-thermal conductive sheet-copper foil" configuration. The 0.15 mm copper foil in the obtained laminate was etched into a circular shape with a diameter of 2 cm, and the laminate was used as a sample for solder heat resistance testing having a configuration of "copper substrate - thermally conductive sheet - circular copper foil with a diameter of 2 cm." The sample was subjected to a heat treatment three times, in which the sample was heated at 300° C. for 5 minutes and then cooled to room temperature (25° C.). After that, the circular copper foil with a diameter of 2 cm was peeled off from the obtained sample. The state of destruction of the peeled samples was visually inspected to determine whether or not interfacial peeling had occurred over part or the entire surface between the copper substrate and the thermally conductive sheet. The solder heat resistance of the thermally conductive sheet was evaluated according to the following classification. A: No interfacial peeling was observed in part or the entire surface between the copper substrate and the thermal conductive sheet. B: Peeling off of the interface was observed in part between the copper substrate and the thermal conductive sheet. C: Interfacial peeling was confirmed over the entire surface between the copper substrate and the thermal conductive sheet.

[0262] [result] The evaluation results are shown in Table 1 below. In the table, the column "(D) / (E)" indicates the mass ratio of the content of aggregated boron nitride to the content of inorganic substance X (content of aggregated boron nitride / content of inorganic substance X).

[0263] [Table 1]

[0264] [Table 2]

[0265] [Table 3]

[0266] The results shown in the table confirm that the effects of the present invention can be achieved by using the composition of the present invention. It was confirmed that the effects of the present invention were more excellent when the mass ratio of the content of aggregated boron nitride to the content of inorganic substance X was 5.0 to 25.0 (comparison of Examples 1 to 3 and 37 to 61). It was confirmed that the effects of the present invention are even better when the composition further contains a surface modifier and the aggregated boron nitride, together with the surface modifier adsorbed on the surface of the aggregated boron nitride, constitute surface-modified aggregated boron nitride (comparison between Examples 22 to 26 and Example 4). It was confirmed that the effects of the present invention are more excellent when either the phenol compound contains a phenol compound having a triazine skeleton or the epoxy compound contains an epoxy compound having a triazine skeleton (comparison between Example 4 and Example 17). It was confirmed that when the composition further contained an ion scavenger, the insulating properties were better (comparison between Examples 4 and 6). It was confirmed that when the composition further contained a maleimide compound, Tg (heat resistance) was superior (comparison between Examples 4 and 5).

Claims

1. containing a phenolic compound, an epoxy compound, aggregated boron nitride, and inorganic substance X; further comprising at least one selected from the group consisting of a maleimide compound and an acid anhydride; At least one of the following requirements is satisfied: the phenol compound contains a phenol compound having a triazine skeleton; and the epoxy compound contains an epoxy compound having a triazine skeleton. the inorganic substance X is at least one selected from the group consisting of aluminum oxide and silicon dioxide, The average particle size of the aggregated boron nitride is 20 μm or more, The curable composition, wherein the inorganic substance X has an average particle size of 0.30 μm or less.

2. The curable composition according to claim 1 , wherein the inorganic substance X has an average particle size of 0.25 μm or less.

3. 3. The curable composition according to claim 1, wherein the mass ratio of the content of the aggregated boron nitride to the content of the inorganic substance X is 5.0 to 25.

0.

4. Further, it contains a surface modifier, 4. The curable composition according to claim 1, wherein the aggregated boron nitride, together with the surface modifier adsorbed on the surface of the aggregated boron nitride, constitutes surface-modified aggregated boron nitride.

5. The curable composition according to any one of claims 1 to 4, further comprising a curing accelerator.

6. The curable composition according to claim 5 , wherein the curing accelerator comprises a compound having a phosphorus atom.

7. The curable composition according to any one of claims 1 to 6, further comprising an ion scavenger.

8. A thermally conductive material obtained by curing the curable composition according to any one of claims 1 to 7.

9. A thermally conductive sheet comprising the thermally conductive material according to claim 8.

10. A device with a thermally conductive layer, comprising: a device; and a thermally conductive layer disposed on the device, the thermally conductive layer comprising the thermally conductive material of claim 8.

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