TW202237689A - Curable composition, thermally conductive material, thermally conductive sheet, device with thermally conductive layer - Google Patents

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 [mu]m or more. The average particle diameter of the inorganic substance X is 0.30 [mu]m or less.

Description

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

The invention relates to a curable composition, a heat conduction material, a heat conduction sheet and a device with a heat conduction layer.

In recent years, the miniaturization of power semiconductor devices used in electronic equipment such as personal computers, general household appliances, and automobiles has been rapidly progressing. Controlling heat generated by high-density power semiconductor devices becomes a problem with miniaturization. In order to solve the above-mentioned problems, thermally conductive materials that promote heat dissipation from power semiconductor devices are being used. For example, Patent Document 1 discloses a thermally conductive composition containing boron nitride or the like.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2013-177562

The inventors of the present invention have studied the composition described in Patent Document 1, etc., and found that there is room for improvement in the thermal conductivity of the obtained thermally conductive material.

Therefore, an object of the present invention is to provide a curable composition capable of forming a thermally conductive material having excellent thermal conductivity. Furthermore, the object of the present invention is to provide a thermally conductive material, a thermally conductive sheet, and a device with a thermally conductive layer related to the above curable composition.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that the above-mentioned problems can be solved by the following configuration.

[1] A curable composition containing a phenolic compound, an epoxy compound, agglomerated boron nitride, and an inorganic substance X, The above-mentioned inorganic substance X is at least one selected from the group consisting of alumina and silicon dioxide, The aggregated boron nitride has an average particle diameter of 20 μm or more, The above-mentioned inorganic substance X has an average particle diameter of 0.30 μm or less. [2] The curable composition according to [1], wherein The above-mentioned inorganic substance X has an average particle diameter of 0.25 μm or less. [3] The curable composition according to [1] or [2], wherein The mass ratio of the content of the above-mentioned aggregated boron nitride to the content of the above-mentioned inorganic substance X is 5.0-25.0. [4] The curable composition according to any one of [1] to [3], which further contains a surface modifier, The above-mentioned condensed boron nitride together with the above-mentioned surface modification agent adsorbed on the surface of the above-mentioned condensed boron nitride constitute surface-modified condensed boron nitride. [5] The curable composition according to any one of [1] to [4], wherein the phenol compound includes a phenol compound having a three-skeleton skeleton and the epoxy compound includes an epoxy compound having a three-skeleton skeleton. at least one of the elements. [6] The curable composition according to any one of [1] to [5], which further contains a curing accelerator. [7] The curable composition according to [6], wherein The above-mentioned hardening accelerator includes a compound having a phosphorus atom. [8] The curable composition according to any one of [1] to [7], which further contains an ion-scavenging agent. [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 described in any one of [1] to [9]. [11] A thermally conductive sheet comprising the thermally conductive material described in [10]. [12] A device with a heat-conducting layer, comprising: a device; and a heat-conducting layer comprising the heat-conducting material described in [10] disposed on the device. [Invention effect]

According to the present invention, it is possible to provide a curable composition capable of forming a thermally conductive material having excellent thermal conductivity. Also, 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 related to the above curable composition.

Hereinafter, the curable composition, thermally conductive material, thermally conductive sheet, and device with a thermally conductive layer of the present invention will be described in detail. The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

Moreover, in this specification, description of "(meth)acryl group" means "any one or both of an acryl group and a methacryl group." In addition, the description of "(meth)acrylamide group" means "any one or both of acrylamide group and methacrylamide group". The description of "(meth)acrylic acid" means "one or both of acrylic acid and methacrylic acid".

In this specification, an acid anhydride group may be a monovalent group or a divalent group. In addition, in the case where the acid anhydride group represents a monovalent group, examples include those obtained by removing arbitrary hydrogen atoms from acid anhydrides such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. the substituent. Moreover, when an acid anhydride group represents a divalent group, it means the group represented by *-CO-O-CO-*. * Indicates bond position. In this specification, unless otherwise specified, the bonding direction of the labeled divalent group (for example, -COO-) is not limited. For example, when Y in the compound represented by "X-Y-Z" is -COO-, the compound may be "X-O-CO-Z" or "X-CO-O-Z".

In this specification, regarding a substituent that is not clearly described as substituted or unsubstituted, if possible, the group may further have a substituent (for example, from a substituent described later) within a range that does not impair the intended effect. Groups exemplified by group Y). For example, the notation "alkyl" refers to a substituted or unsubstituted alkyl group (an alkyl group that may have a substituent) within the range that does not impair the intended effect. In the present specification, when "may have a substituent", the kind of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. As the number of substituents, for example, one or two or more are mentioned. As the substituent, for example, a monovalent non-metallic atomic group other than a hydrogen atom can be mentioned, and a group selected from the substituent group Y is preferable. In the present specification, examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

(Substituent group Y) Halogen atom (-F, -Br, -Cl and -I, etc.), hydroxyl group, amine group, carboxylic acid group and its conjugate base, carboxylic anhydride group, cyanate group, unsaturated Polymerization group, epoxy group, oxetanyl group, aziridine group, thiol group, isocyanate group, thioisocyanate group, aldehyde group, alkoxy group, allyloxy group, alkylthio group, arylthio group Alkyldithiol, aryldithiol, N-alkylamino, N,N-dialkylamino, N-arylamino, N,N-diarylamino, N- Alkyl-N-arylamino, acyloxy, aminoformyloxy, N-alkylaminoformyloxy, N-arylaminoformyloxy, N,N-dialkylaminoformyl Oxygen, N,N-Diarylaminoformyloxy, N-Alkyl-N-arylaminoformyloxy, Alkylsulfoxyl, Arylsulfoxyl, Acylthio, Amide , N-alkylamide group, N-arylamide group, ureido group, N'-alkylureido group, N',N'-dialkylureido group, N'-arylureido group, N',N'-diaryl ureido, N'-alkyl-N'-aryl ureido, N-alkyl ureido, N-aryl ureido, N'-alkyl-N-aryl ureido , N'-alkyl-N-aryl ureido, N',N'-dialkyl-N-alkyl ureido, N',N'-dialkyl-N-aryl ureido, N' -aryl-N-alkylureido, N'-aryl-N-arylureido, N',N'-diaryl-N-alkylureido, N',N'-diaryl -N-aryl ureido, N'-alkyl-N'-aryl-N-alkyl ureido, N'-alkyl-N'-aryl-N-aryl ureido, alkoxycarbonyl Amino, Allyloxycarbonylamino, N-Alkyl-N-Alkoxycarbonylamino, N-Alkyl-N-allyloxycarbonylamino, N-Aryl-N-Alkoxy Carbonylamino, N-aryl-N-allyloxycarbonylamino, formyl, acyl, alkoxycarbonyl, allyloxycarbonyl, aminoformyl, N-alkylaminoformyl , N,N-dialkylaminoformyl, N-arylaminoformyl, N,N-diarylaminoformyl, N-alkyl-N-arylaminoformyl, alkyl Sulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO ₃ H) and its conjugate base, alkoxysulfonyl, allyloxy Sulfonyl, Aminosulfinyl, N-Alkylaminesulfinyl, N,N-Dialkylaminesulfinyl, N-Arylaminesulfinyl, N,N-Diaryl Aminosulfinyl, N-Alkyl-N-arylaminesulfinyl, Aminosulfonyl, N-Alkylaminosulfonyl, N,N-Dialkylaminosulfonyl, N-aryl Aminosulfonyl, N,N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-acylsulfamoyl and its conjugate base, N-alkane Sulfonylsulfamoyl (-SO ₂ NHSO ₂ (alkyl)) and its conjugate base, N-arylsulfamosulfonyl (-SO ₂ NHSO ₂ (aryl)) and its Conjugated base, N-alkylsulfonylaminoformyl (-CONHSO ₂ (alkyl)) and its conjugate base, N-arylsulfonylaminoformyl (-CON HSO ₂ (aryl)) and its conjugate base, alkoxysilyl (-Si(O-alkyl) ₃ ), allyloxysilyl (-Si(O-aryl) ₃ ) , hydroxysilyl group (-Si(OH) ₃ ) and its conjugated base, phosphonyl group (-PO ₃ H ₂ ) and its conjugated base, dialkylphosphonyl group (-PO ₃ (alkyl ) ₂ ), diarylphosphinoyl (-PO ₃ (aryl) ₂ ), alkylarylphosphinoyl (-PO ₃ (alkyl)(aryl)), monoalkylphosphinoyl (- PO ₃ H (alkyl)) and its conjugated base, monoarylphosphonyl (-PO ₃ H (aryl)) and its conjugated base, phosphonyloxy (-OPO ₃ H ₂ ) and Its conjugate base, dialkylphosphonyloxy (-OPO ₃ (alkyl) ₂ ), diarylphosphonyloxy (-OPO ₃ (aryl) ₂ ), alkylarylphosphonyloxy (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonyloxy (-OPO ₃ H (alkyl)) and its conjugate base, monoarylphosphonyloxy (-OPO ₃ H (aryl)) and their conjugated bases, cyano, nitro, aryl, alkenyl, alkynyl and alkyl. Also, each of the above-mentioned groups may further have a substituent (for example, one or more of the above-mentioned groups) if possible. For example, the group that can be selected from the substituent group Y also includes an aryl group that may have a substituent. When the group selected from the substituent group Y has carbon atoms, 1 to 20 are preferable as the carbon number of the above-mentioned group. 1-30 are preferable as the number of atoms other than a hydrogen atom which the group selected from substituent group Y has. Also, if possible, these substituents may form a ring by bonding each other or a substituted group, or may not form a ring. For example, an alkyl group (or an alkyl part in a group including an alkyl group as a partial structure such as an alkoxy group) may be a cyclic alkyl group (cycloalkyl group), or may have 1 Alkyl groups with more than one ring structure.

[composition] The curable composition of the present invention (hereinafter also simply referred to as "composition") contains a phenolic compound, an epoxy compound, agglomerated boron nitride, and an inorganic substance X described later, and the average particle size of the agglomerated boron nitride is 20 μm or more , the average particle diameter of the inorganic substance X is 0.30 μm or less. Hereinafter, the aggregated boron nitride having an average particle diameter of 20 μm or more and the inorganic substance X having an average particle diameter of 0.30 μm or less are also simply referred to as specific inorganic substances.

Although the mechanism by which the subject of this invention is solved by the said structure is not clear, the inventors of this invention presume as follows. The average particle diameter of the inorganic substance X with the predetermined particle diameter is smaller than the average particle diameter of the aggregated boron nitride with the predetermined particle diameter. In the thermally conductive material, such an inorganic substance X can exist between predetermined condensed boron nitrides and the like. As a result, it is presumed that in the thermally conductive material, the voids between the specific inorganic substances are reduced, so that the thermal conductivity is excellent. Hereinafter, the excellent thermal conductivity of the thermally conductive material formed by using the composition is also referred to as the excellent effect of the present invention.

Hereinafter, the components contained in the composition will be described in detail.

〔Phenolic compound〕 The composition of the present invention contains a phenolic compound. The 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, more preferably 2-10. It is preferable that the phenolic compound has a three-skeleton structure. "Having a trioxane skeleton" means that the phenol compound has one or more (for example, 1 to 5) trioxane ring groups in the compound.

(compound represented by formula (Z)) The phenolic compound is preferably a compound represented by formula (Z).

[chemical formula 1]

In the above formula (Z), when there are plural groups represented by the same symbol, unless otherwise specified, the plural groups represented by the same symbol may be the same or different, respectively.

In formula (Z), E ¹ to E ⁶ each independently represent a single bond, -NH- or -NR-. As E ¹ to E ⁶ , each independently being -NH- or -NR- is preferable, and -NH- is more preferable. R represents a substituent. Examples of the substituent represented by R include linear or branched alkyl groups having 1 to 5 carbon atoms.

In formula (Z), B ¹ represents a single bond or a k+1-valent organic group. B ² represents a single bond or a 1+1-valent organic group. B ³ represents a single bond or an m+1-valent organic group. B ⁴ represents a single bond or an n+1-valent organic group. The value of k, l, m and n in the above-mentioned k+1 valent organic group, the above-mentioned l+1 valent organic group, the above-mentioned m+1 valent organic group and the above-mentioned n+1 valent organic group and the formula (Z ) in k, l, m and n have the same value. In addition, when r is 2 or more and there are a plurality of different values of m, the difference between the value of m in the m+1-valent organic group represented by ^B3 and the number of ^X3 to which ^B3 is bonded The value of m is the same.

Examples of the organic groups represented by B ¹ to B ⁴ include groups obtained by removing j hydrogen atoms from hydrocarbons which may have heteroatoms having 1 to 20 carbon atoms. In addition, j means k+1, l+1, m+1 or n+1. Among them, as the hydrocarbon before j hydrogen atoms are removed, for example, 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 One or more hydrocarbons in the group of aromatic rings having 3 to 20 carbon atoms which may have a substituent. Also, for the group obtained by removing j hydrogen atoms from the above-mentioned hydrocarbon, it may be further selected from the group including -O-, -S-, -CO-, -NR ^N - and -SO ₂ - A group formed by combining one or more of the divalent linking groups. R ^N represents a hydrogen atom or a substituent. Examples of the 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 the aromatic ring having 3 to 20 carbon atoms include an aromatic hydrocarbon ring having 6 to 20 carbon atoms and an aromatic heterocyclic ring 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 the aromatic heterocyclic ring 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.

In formula (Z), k, l, m, and n each independently represent an integer of 0 or more. However, the total of k, l, r×m, and n is 2 or more, preferably an integer of 2-12, more preferably an integer of 4-8. In addition, the value of m in "rxm" is the average value of m which may exist in plural. Preferably, k, l, m, and n are each independently 0-5, and more preferably 1-2. Among them, k is preferably 1 or more (for example, 1-2), l is 1 or more (for example, 1-2) is better, m is 1 or more (for example, 1-2) is better, n is 1 The above (for example, 1 to 2) are preferable. Also, when k is 0, B ¹ does not have X ¹ . When l is 0, B ² does not have X ² . When m is 0, B ³ does not have X ³ . When n is 0, B ⁴ does not have X ⁴ . Also, when B ¹ is a single bond, k is 1. When B ² is a single bond, l is 1. When B ³ is a single bond, m is 1. When B ⁴ is a single bond, n is 1.

L represents a divalent organic group. Examples of the divalent organic group include an optionally substituted aromatic ring group, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic ring group, -O-, -S-, -N (R ^N )-, -CO- and a combination thereof. R ^N represents a hydrogen atom or a substituent. Examples of the substituent represented by R ^N include straight-chain alkyl groups and branched-chain alkyl groups having 1 to 5 carbon atoms. Moreover, as a substituent which may have an aromatic ring group, an aliphatic hydrocarbon group, and an aliphatic ring group represented by L, a C1-C5 straight-chain alkyl group and a branched-chain alkyl group are mentioned, for example.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms. Examples of the aromatic hydrocarbon ring group having 6 to 20 carbon atoms include groups obtained by removing two hydrogen atoms from the aromatic ring. Examples of the aromatic ring include monocyclic aromatic rings such as benzene rings and polycyclic aromatic rings such as naphthalene rings and anthracene rings. Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include groups obtained by removing two hydrogen atoms from the aromatic heterocyclic ring. 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 benzothiazole rings, carbazole rings, and indole rings. Polycyclic aromatic heterocycles.

Examples of aliphatic hydrocarbon groups include alkylene groups having 1 to 12 carbon atoms, specifically, methylene groups, ethylene groups, propylidene groups, butylene groups, pentylene groups, hexylene groups, Methylhexyl and heptyl, etc.

As an aliphatic ring group, the group which removed 2 hydrogen atoms from an aliphatic ring is mentioned, for example. As said aliphatic ring, a cyclohexane ring, a cycloheptane ring, a norbornane ring, an adamantane ring, etc. are mentioned, for example.

An aromatic ring group that may have a substituent, an aliphatic hydrocarbon group that may have a substituent, an aliphatic ring group that may have a substituent, or a combination of -O-, -S-, -NR ^N - or -CO- The group may not only be a divalent linking group consisting of two or more of these combinations, but may also be a combination of two or more of the same type of group (for example, an aromatic ring group) via a single bond. bivalent linker.

From the point of view of better thermal conductivity of the thermally conductive material, it is preferable that both terminals of L are carbon atoms. The terminal carbon atoms may be part of a ring structure. Also, from the viewpoint of better thermal conductivity of the thermally conductive material, L in the above formula (Z) is a divalent aromatic ring group selected from a divalent aromatic ring group that may have a substituent, a divalent aliphatic ring group that may have a substituent, and At least one divalent organic group in the group of alkylene groups that may have a branched chain having 2 or more carbon atoms is preferred, and has a divalent aromatic ring that may have a substituent in view of better thermal conductivity. The divalent organic group of the base is more preferable.

In formula (Z), r is an integer of 0 or more. r is preferably an integer of 0-20, more preferably an integer of 0-10.

In formula (Z), X ¹ to X ⁴ each independently represent an aromatic ring group having a phenolic hydroxyl group. The "aromatic ring group having a phenolic hydroxyl group" should just be an aromatic ring group having one or more (for example, 1 to 4) hydroxyl groups (phenolic hydroxyl groups) directly bonded to an aromatic ring. The above-mentioned aromatic ring group may or may not have a substituent other than the above-mentioned hydroxyl group. The aforementioned aromatic ring group may be monocyclic or polycyclic, and may have a heteroatom as a ring member atom. The number of ring member atoms of the aromatic ring group is preferably 5-15, more preferably 6-10, and still more preferably 6. As the above-mentioned aromatic ring group, a phenyl ring group is preferable. As the substituent that the above-mentioned aromatic ring group may have in addition to the above-mentioned hydroxyl group, a substituent having 1 to 6 carbons is preferable, a hydrocarbon group having 1 to 6 carbons is more preferable, and a linear or branched chain having 1 to 6 carbons is more preferable. The like alkyl group is further preferred.

In formula (Z), at least one of k X ¹ , l X ² , r×m X ³ and n X ⁴ has a phenolic hydroxyl group and is arranged in a phenolic hydroxyl group. The aromatic ring group of the substituent at the ortho position of the hydroxyl group is also preferable. The above-mentioned substituent may exist only in one ortho-position of the above-mentioned phenolic hydroxyl group, and may exist in two ortho-positions. In addition, the value of m in "rxm" is the average value of m which may exist in plural. In addition, the "substituent arranged at the ortho position" is preferably a substituent having 1 to 6 carbons, more preferably a hydrocarbon group having 1 to 6 carbons, and a linear or branched alkyl having 1 to 6 carbons. The base is further preferred. In other words, at least one (preferably 30% or more) of the "aromatic ring group having a phenolic hydroxyl group" represented by any one of (k+l+r×m+n) X ¹ to X ⁴ , more preferably more than 50%, more preferably more than 65%. Preferably less than 100%, more preferably less than 90%, more preferably less than 80%) can mean "having phenolic hydroxyl and disposing in phenolic The aromatic ring group of the substituent at the ortho position of the hydroxyl group".

Among the aromatic ring groups having phenolic hydroxyl groups represented by X ¹ to X ⁴ , the aromatic ring group other than the "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" may have Or it does not have a substituent other than a hydroxyl group (phenolic hydroxyl group). As an aromatic ring group other than "the aromatic ring group which has a phenolic hydroxyl group and the substituent arrange|positioned at the ortho position of a phenolic hydroxyl group", a hydroxyphenyl group is mentioned, for example. Among the "aromatic ring groups having a phenolic hydroxyl group" represented by any one of (k+l+r×m+n) X ¹ to X ⁴ , at least one (for example, 1 to 2) is An aromatic ring group other than "the aromatic ring group which has a phenolic hydroxyl group and the substituent arrange|positioned at the ortho position to a phenolic hydroxyl group" is also preferable. It is considered that among the aromatic ring groups having phenolic hydroxyl groups represented by X ¹ to X ⁴ , aromatic ring groups other than "aromatic ring groups having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" are present. The ring group will break the symmetry of the compound as a whole, lower the melting point of the compound and improve the operability of the semi-hardened film formed by the composition.

(compound represented by formula (Z1)) It is also preferable that the phenolic compound is a compound represented by formula (Z1). The phenolic compound preferably includes a compound represented by formula (Z1), and the phenolic compound itself may be a compound represented by formula (Z1). The content of the compound represented by the formula (Z1) is preferably from 10 to 100% by mass, more preferably from 25 to 100% by mass, and still more preferably from 50 to 100% by mass, based on the total mass of the phenolic compounds.

[chemical formula 2]

In formula (Z1), r represents an integer of 0 or more. r is preferably an integer of 0-20, more preferably an integer of 0-10. 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. As the substituent represented by R ^Z , a substituent having 1 to 6 carbons is preferable, a hydrocarbon group having 1 to 6 carbons is more preferable, and a linear or branched alkyl group having 1 to 6 carbons is further preferable. better. At least one (30% or more, more preferably 50% or more, further preferably 65% or more, preferably 90% or less) of (3+r) R ^Z in the formula (Z1), More preferably 80% or less) may represent a substituent. At least one (eg, 1 to 2) of (3+r) R ^Z in the formula (Z1) may represent a hydrogen atom. Among R ^z (preferably substituent R ^z ) in formula (Z1) and the phenyl ring group bonded to OH, the above R ^z (preferably substituent R ^z ) exists in the bonded phenyl ring group The para position of NH is also better.

(compound represented by formula (Z2)) It is also preferable that the phenolic compound is a compound represented by formula (Z2). The phenolic compound preferably includes a compound represented by formula (Z2), and the phenolic compound itself may be a compound represented by formula (Z2). The content of the compound represented by the formula (Z2) is preferably from 10 to 100% by mass, more preferably from 25 to 100% by mass, and still more preferably from 50 to 100% by mass, based on the total mass of the phenolic compounds.

[chemical formula 3]

In formula (Z2), R ^Z represents a hydrogen atom or a substituent. It is also preferable that at least one of R ^Z present in two represents a substituent, and it is also preferable that two represent a substituent. The substituent represented by R ^Z is preferably a substituent having 1 to 6 carbons, more preferably a hydrocarbon group having 1 to 6 carbons, and still more preferably an alkyl group having 1 to 6 carbons. The above-mentioned alkyl group may be linear or branched. It is also preferable that the above-mentioned alkyl group is unsubstituted. The two R ^z in the formula (Z2) may be the same or different.

As a phenolic compound, other than the above, you may contain other phenolic compounds. Examples of other phenolic compounds include bisphenol A, F, S, AD, benzene polyols such as benzenediol and benzenetriol, biphenyl aralkyl type phenol resins, phenol novolak resins, cresol novolaks, etc. Resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, polyvalent phenol novolac resin synthesized from polyvalent hydroxyl compounds and formaldehyde, naphthol aralkyl resin , trimethylolmethane resin, tetraphenol-based ethane resin, naphthol phenol novolac resin, naphthol phenol co-reduced novolac resin, naphthol-cresol co-derivative novolak resin, biphenyl modified phenol resin, biphenyl modified Quality naphthol resins, amino-modified phenol resins and aromatic ring-modified novolak resins containing alkoxy groups.

The molecular weight of the phenolic compound is preferably 225-2000, more preferably 225-1000. In addition, when the said molecular weight exists molecular weight distribution, the said molecular weight is a weight average molecular weight.

The hydroxyl group content of the phenolic compound is preferably at least 2.0 mmol/g, more preferably at least 4.0 mmol/g. The upper limit is preferably at most 25.0 mmol/g, more preferably at most 10.0 mmol/g. In addition, the said hydroxyl group content means the number of the hydroxyl group (preferably phenolic hydroxyl group) which 1 g of phenolic compounds have. In addition, the phenol compound may or may not have an active hydrogen-containing group (carboxylic acid group, etc.) capable of polymerization reaction with the epoxy compound in addition to the hydroxyl group. The lower limit of the active hydrogen content (the total content of hydrogen atoms in hydroxyl groups, carboxylic acid groups, etc.) of the phenolic compound is preferably 2.0 mmol/g or more, more preferably 4.0 mmol/g or more. The upper limit is preferably at most 25.0 mmol/g, more preferably at most 10.0 mmol/g.

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

A phenolic compound may be used individually by 1 type, and may use 2 or more types. The content of the phenolic compound is preferably from 3.0 to 90.0% by mass, more preferably from 5.0 to 50.0% by mass, still more preferably from 7.0 to 40.0% by mass, and particularly preferably from 7.0 to 15.0% by mass, based on the total solid content of the composition. The above-mentioned solid component means a component that forms a thermally conductive material, and does not include a solvent. In addition, the components that form the thermally conductive material may be components that react (polymerize) when forming the thermally conductive material to change the chemical structure. Moreover, as long as it is a component which forms a thermally conductive material, even if its property is liquid, it is considered as a solid component.

〔Epoxy compound〕 The composition of the present invention contains an epoxy compound. The 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. The above-mentioned epoxy group may further have a substituent (linear or branched C 1-5 alkyl group, etc.) if possible.

It is preferable that the number of the epoxy groups which an epoxy compound has is 2 or more in 1 molecule, 2-1000 are more preferable, 2-40 are still more preferable.

The molecular weight of the epoxy compound is preferably 150 or more, more preferably 300 or more. The upper limit is preferably 100,000 or less, more preferably 10,000 or less. In addition, when the said molecular weight exists molecular weight distribution, the said molecular weight is a weight average molecular weight. In the present specification, the number average molecular weight and the weight average molecular weight are weight average molecular weights obtained in terms of polystyrene by gel permeation chromatography (GPC).

The epoxy group content of the epoxy compound is preferably 2.0-20.0 mmol/g, more preferably 5.0-15.0 mmol/g. In addition, the said epoxy group content means the number of the epoxy group which 1g of epoxy compounds have. It is also preferable that the epoxy compound has an aromatic ring group (preferably an aromatic hydrocarbon ring group).

The epoxy compound may or may not exhibit liquid crystallinity. That is, the epoxy compound may be a liquid crystal compound. In other words, it may be a liquid crystal compound having an epoxy group. Examples of epoxy compounds (which may also be liquid crystalline epoxy compounds) include compounds at least partially containing a rod-like structure (rod-shaped compound) and compounds at least partially containing a disc-like structure (disco-shaped compound). compound). Hereinafter, the rod-shaped compound and the discotic compound will be described in detail.

(Rod-shaped compound) Examples of the epoxy compound to be a rod-shaped compound include azomethines, oxazos, cyanobiphenyls, cyanophenyl esters, benzoate esters, cyclohexyl Phenyl alkanecarboxylates, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanylacetylenes and alkenylcyclohexyl Bian nitriles. Not only low-molecular compounds as described above but also high-molecular compounds can be used. The above-mentioned high molecular compound is a high molecular compound obtained by polymerizing rod-shaped compounds having low molecular reactive groups. Preferred rod-shaped compounds include rod-shaped compounds represented by the following formula (XXI). Formula (XXI): Q ¹ -L ¹¹¹ -A ¹¹¹ -L ¹¹³ -ML ¹¹⁴ -A ¹¹² -L ¹¹² -Q ²

In formula (XXI), Q ¹ and Q ² are each independently an epoxy group, and L ¹¹¹ , L ¹¹² , L ¹¹³ , and L ¹¹⁴ each independently represent a single bond or a divalent linking group. A ¹¹¹ and A ¹¹² each independently represent a divalent linking group (spacer) having 1 to 20 carbon atoms. M represents a liquid crystal group. ^The epoxy groups of Q1 and ^Q2 may or may not have a substituent.

In formula (XXI), L ¹¹¹ , L ¹¹² , L ¹¹³ and L ¹¹⁴ each independently represent a single bond or a divalent linking group. The divalent linking groups represented by L ¹¹¹ , L ¹¹² , L ¹¹³ and L ¹¹⁴ are each independently selected from the group consisting of -O-, -S-, -CO-, -NR ¹¹² -, -CO-O-, The divalent linking group in the group of -O-CO-O-, -CO-NR ¹¹² -, -CH ₂ -O-, -O-CO-NR ¹¹² - and -NR ¹¹² -CO-NR ¹¹² - is better. The above-mentioned R ¹¹² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. Among them, L ¹¹³ and L ¹¹⁴ are preferably each independently -O-. L ¹¹¹ and L ¹¹² are preferably each independently a single bond.

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

In the formula (XXI), M represents a liquid crystal group. Examples of the liquid crystal group include known liquid crystal groups. Among them, a group represented by the following formula (XXII) is preferable. Formula (XXII): -(W ¹ -L ¹¹⁵ ) _n -W ² -

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

Examples of W ¹ and W ² 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 thiamine-3,6-diyl. In the case of 1,4-cyclohexanediyl, it may be any one of the structural isomers of the trans-isomer and the cis-isomer, or may be a mixture in any ratio. Among them, the trans form is preferred. W ¹ and W ² may each have a substituent. As the substituent, for example, the groups exemplified in the substituent group Y described above, more specifically, halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom), cyanide group, alkyl group with 1 to 10 carbons (for example, methyl, ethyl and propyl, etc.), alkoxy group with 1 to 10 carbons (for example, methoxy and ethoxy group, etc.), carbon number with 1 to 10 Acyl group with 10 (such as formyl and acetyl, etc.), alkoxycarbonyl with 1 to 10 carbons (such as methoxycarbonyl and ethoxycarbonyl, etc.), acyloxy with 1 to 10 carbons (for example, acetyloxy and propionyloxy, etc.), nitro, trifluoromethyl and difluoromethyl. When there are plural W ¹ s, the plural W ¹ present may be the same or different.

In formula (XXII), L ¹¹⁵ represents a single bond or a divalent linking group. Specific examples of the divalent linking group represented by L ¹¹¹ to L ¹¹⁴ described above as the divalent linking group represented by L ¹¹⁵ include -CO-O-, -CH ₂ -O -. When there are plural L ¹¹⁵ , the plural L ¹¹⁵ may be the same or different.

Among the basic skeletons of the liquid crystal group represented by the above formula (XXII), preferable skeletons are shown below. The above mesogenic groups may also be substituted with substituents in these skeletons.

[chemical formula 4]

[chemical formula 5]

Among them, a biphenyl skeleton is preferable as the above-mentioned liquid crystal base from the viewpoint that the thermal conductivity of the obtained thermally conductive material is more excellent. In addition, the compound represented by formula (XXI) can be synthesized by referring to the method described in JP-A-11-513019 (WO97/00600). The rod-shaped compound may be a monomer having a liquid crystal group described in JP-A-11-323162 and JP-A-4118691.

Also, among the compounds represented by the formula (XXI), one or both of "Q ¹ -L ¹¹¹ -" and "-L ¹¹² -Q ² " is substituted by a diecidylamine group. good.

Among them, the rod-shaped compound is preferably a compound represented by formula (E1).

[chemical formula 6]

In the formula (E1), L ^E1 each independently represent a single bond or a divalent linking group. Among them, L ^E1 is preferably a divalent linking group. The divalent linking group is -O-, -S-, -CO-, -NH-, -CH=CH-, -C≡C-, -CH=N-, -N=N-, and may have a substituent An alkylene group or a group consisting of two or more of these combinations is preferable, and -O-alkylene group- is more preferable. In addition, the above-mentioned alkylene group may be any of linear, branched, and cyclic, and a linear alkylene group having 1 to 2 carbon atoms is preferred. Plural L ^E1 may be the same or different.

In the formula (E1), L ^E2 independently represent a single bond, -CH=CH-, -CO-O-, -C(-CH ₃ )=CH-, -CH=N-, -N=N-, -C≡C-, -N=N ⁺ (-O ^- )-, -CH=N ⁺ (-O ^- )-, -CH=CH-CO-, or -CH=C(-CN)-. Among them, it is preferable that L ^E2 are each independently a single bond or -CO-O-. When there are plural L ^E2 , the plural L ^E2 may be the same or different.

In formula (E1), L ^E3 independently represents a single bond or a 5-membered or 6-membered aromatic ring group that may have a substituent, a 5-membered or 6-membered ring non-aromatic ring group, or consists of these rings The polycyclic group. Examples of the aromatic ring group and non-aromatic ring group represented by L ^E3 include 1,4-cyclohexanediyl, 1,4-cyclohexenediyl, 1,4-xene Phenyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3,4-thiadiazol-2,5-diyl, 1,3,4-oxadiazole-2, 5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, and naphthalene-3,6-diyl. In the case of 1,4-cyclohexanediyl, it may be any one of the structural isomers of the trans-isomer and the cis-isomer, or may be a mixture in any ratio. Among them, the trans form is preferred. Among them, L ^E3 is preferably a single bond, 1,4-phenylene group or 1,4-cyclohexenediyl group. The substituents of the group represented by L ^E3 are independently alkyl, alkoxy, halogen atom, cyano, nitro or acetyl group, and alkyl (preferably methyl) is more preferred. good. In addition, when a plurality of substituents exist, the substituents may be respectively the same or different. When there are plural L ^E3s , the plural L ^E3s may be the same or different.

In formula (E1), pe represents an integer of 0 or more. When pe is an integer greater than or equal to 2, there are a plurality of (-L ^E3 -L ^E2 -) which may be the same or different. Among them, pe is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

In formula (E1), L ^E4 each independently represent a substituent. The substituents are each independently an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group or an acetyl group, and an alkyl group (preferably a methyl group) is more preferable. The plural L ^E4 may be the same or different. In addition, when le described later is an integer of 2 or more, plural L ^E4 existing in the same (L ^E4 ) _le may be the same or different.

In formula (E1), le represents the integer of 0-4 each independently. Among them, le is preferably 0-2 each independently. Plural le may be the same or different.

In addition, in the compound represented by formula (E1), one or both of the two "epoxy groups -L ^E1 -" are substituted by diglycidylamino alkylene (preferably bicyclic Oxypropylaminomethylene) compounds are also preferred.

It is also preferable that the rod-shaped compound has a biphenyl skeleton from the viewpoint of the thermal conductivity of the obtained thermally conductive material being more excellent. In other words, it is also preferable that the epoxy compound has a biphenyl skeleton, and it is preferable that the epoxy compound is a rod-shaped compound at this time.

(disc-shaped compound) Epoxy compounds which are discotic compounds at least partially have a discotic structure. The disc-shaped structure has at least an alicyclic ring or an aromatic ring. In particular, in the case where the discotic structure has an aromatic ring, the discotic compound can form a columnar structure by forming a stacked structure based on π-π interactions between molecules. As the disk-shaped structure, for example, Angew.Chem.Int.Ed. 2012, 51, 7990-7993 and the biterphenyl structure described in JP 7-306317 and JP 2007- 002220 Gazette and the trisubstituted benzene structure described in JP 2010-244038 Gazette, etc.

When a disc-shaped compound is used as the epoxy compound, a thermally conductive material exhibiting high thermal conductivity can be obtained. The reason for this is considered to be that the rod-shaped compound can only conduct heat linearly (one-dimensionally), but the disc-shaped compound can conduct heat planarly (two-dimensionally) along the normal direction, so that the heat conduction path increases and the thermal conductivity is improved.

It is preferable that the above-mentioned discotic compound 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 that the discotic compound has is preferably 8 or less, more preferably 6 or less. The lower limit is preferably 2 or more, more preferably 3 or more.

Examples of discotic compounds include C. Destrade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981); edited by the Chemical Society of Japan, Quarterly Journal of Chemistry, No. 22 , Liquid Crystal Chemistry, 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 the compounds described in Japanese Patent No. 4592225 have at least one (preferably three or more) of the terminals as epoxy groups compound. As discotic compounds, for example, Angew. Chem. Int. Ed. 2012, 51, 7990-7993 and the biterphenyl structure described in JP-A No. 7-306317 and JP-A 2007- Among the trisubstituted benzene structures described in Publication No. 002220 and Japanese Patent Application Laid-Open No. 2010-244038, at least one (preferably three or more) of the terminals is a compound having an epoxy group.

As a discotic compound, the compound represented by any one of the formulas (D1)-(D16) shown below is preferable from a viewpoint of the thermal conductivity of a thermally conductive material being more excellent. In addition, in formulas (D1) to (D16), "-LQ" represents "-L-Q", and "QL-" represents "Q-L-".

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

In formulas (D1) to (D15), L represents a divalent linking group. From the point of view that the thermal conductivity of the thermally conductive material is more excellent, as L, each independently is an alkylene group, an alkenylene group, an arylylene group, -CO-, -NH-, -O-, -S-, and is selected from the group consisting of The groups in the group of these combinations are preferred, and a combination of two or more groups selected from the group consisting of alkylene, alkenylene, aryl, -CO-, -NH-, -O- and -S- The group formed by the group in the group is more preferable. It is preferable that the carbon number of the said alkylene group is 1-12. It is preferable that the carbon number of the said alkenylene group is 2-12. It is preferable that the carbon number of the above-mentioned arylylene group is 6-10. The above-mentioned alkylene group, the above-mentioned alkenylene group, and the above-mentioned arylylene group may have a substituent (preferably an alkyl group, a halogen atom, a cyano group, an alkoxy group, or an acyloxy group, etc.).

As L, the groups represented by L101-L143 are mentioned, for example. In the following, the bond on the left side is bonded to the central structure (hereinafter, also simply referred to as "central ring") of the compound represented by any of the formulas (D1) to (D15), and the bond on the right side is Ended with Q. AL represents an alkylene or alkenylene group, and AR represents an arylylene group. The alkylene group represented by AL may be linear or branched. It is preferable that the carbon number of the said alkylene group is 1-12. The alkenylene group represented by AL may be linear or branched. It is preferable that the carbon number of the said alkenylene group is 2-12. The arylylene group represented by AR may be monocyclic or polycyclic. The above-mentioned aryl group preferably has 6-12 ring member atoms.

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-

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-

In formulas (D1) to (D15), Q each independently represent a hydrogen atom or a substituent. Examples of the substituent include groups exemplified in the substituent group Y described above. More specifically, examples of substituents include the above-mentioned reactive functional groups, halogen atoms, isocyanate groups, cyano groups, unsaturated polymerizable groups, epoxy groups, oxetanyl groups, aziridinyl groups, sulfur Substituted isocyanate group, aldehyde group and sulfo group. Among them, when Q is a group other than epoxy group, it is preferable that Q is stable with respect to epoxy group. In addition, in the formulas (D1) to (D15), one or more (preferably two or more) Qs represent epoxy groups. Among them, from the viewpoint that the heat conductivity of the heat conduction material is more excellent, it is preferable that all Qs represent an epoxy group. Moreover, it is preferable that the compound represented by formula (D1) - (D15) does not have -NH- from a viewpoint of the stability of an epoxy group.

Among them, the compound represented by the formula (D4) is preferable as the disc-shaped compound from the viewpoint that the thermal conductivity of the heat-conducting material is more excellent. In other words, it is preferable that the central ring of the disc-shaped compound is a bi-extended triphenyl ring. It is preferable that the compound represented by the formula (D4) is a compound represented by the formula (XI) from the viewpoint that the thermal conductivity of the heat-conducting material is more excellent.

[chemical formula 11]

In formula (XI), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent *-X ¹¹ -L ¹¹ -P ¹¹ or *-X ¹² -L ¹² -Y ¹² . In addition, * represents the bonding position with the extended triphenyl ring. Among R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , two or more are *-X ¹¹ -L ¹¹ -P ¹¹ , and three or more are *-X ¹¹ -L ¹¹ -P ¹¹ good. Among them, from the viewpoint of better thermal conductivity of the heat-conducting material, any one or more of ^R11 and ^R12 , any one or more of ^R13 and ^R14 , and any one or more of ^R15 and ^R16 are *-X ¹¹ -L ¹¹ -P ¹¹ is preferred. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all *-X ¹¹ -L ¹¹ -P ¹¹ is more preferred. In addition, it is further preferred that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all the same.

X ¹¹ independently represent 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 ¹¹ is independently -O-, -O-CO-O-, -O-CO-NH-, -CO-O- or -CO-NH- is preferably, -O-, -CO- O- or -O-CO-NH- is more preferable, and -CO-O- is still more preferable.

L ¹¹ each independently represent a single bond or a divalent linking group. As examples of divalent linking groups, for example, -O-, -CO-O-, -S-, -NH-, alkylene groups (preferably 1 to 10 carbons, more preferably 1 to 8 carbons) Preferably, 1-7 is more preferably.), aryl (6-20 carbon number is more preferable, 6-14 is more preferable, 6-10 is further preferable.) and the group consisting of these combinations group. Examples of the above-mentioned alkylene group include methylene group, ethylene group, propylidene group, butylene group, pentylene group, hexylene group and heptylene group. As the above-mentioned arylylene group, for example, 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group and anthracenyl group, 1,4- -Phenylylene is preferred.

The above-mentioned alkylene group and the above-mentioned arylylene group may each have a substituent. The number of substituents is preferably 1 to 3, more preferably 1. The substitution position of the substituent is not particularly limited. As the substituent, a halogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. It is also preferable that the above-mentioned alkylene group and the above-mentioned arylylene group are unsubstituted. Among them, it is preferable that the alkylene group is unsubstituted.

Examples of -X ¹¹ -L ¹¹ - include examples L101 to L143 of L described above.

P ¹¹ represents an epoxy group. The said epoxy group may have a substituent, and may not have a substituent.

^X12 is the same as ^X11 , and the preferred conditions are also the same. L ¹² is the same as L ¹¹ , and the preferred conditions are also the same. Examples of -X ¹² -L ¹² - include examples L101 to L143 of L mentioned above.

Y ¹² represents a hydrogen atom, a straight chain with 1 to 20 carbons, a branched chain with 1 to 20 carbons, a cyclic alkyl group with 1 to 20 carbons, a straight chain with 1 to 20 carbons, a carbon number One or more methylene groups in a branched-chain or cyclic alkyl group with 1 to 20 carbon atoms are replaced by -O-, -S-, -NH-, -N(CH ₃ )- , -CO- or -CO-O-substituted groups. In Y ¹² , it is a straight chain with 1 to 20 carbons, a branched chain with 1 to 20 carbons, or a cyclic alkyl group with 1 to 20 carbons, or a straight chain with 1 to 20 carbons, with 1 to 20 carbons. One or two or more methylene groups in a 20-branched or cyclic alkyl group with 1 to 20 carbons are replaced by -O-, -S-, -NH-, -N(CH ₃ )-, - In the case of a CO- or -CO-O-substituted group, one or more hydrogen atoms contained in Y ¹² may be substituted with a halogen atom.

Examples of the compound represented by the formula (XI) include paragraphs [0028] to [0036] of JP-A-7-281028, JP-A-7-306317, and JP-A-2005-156822. Among the compounds described in paragraphs [0016] to [0018] of Japanese Patent Application Laid-Open No. 2006-301614, paragraphs [0067] to [0072] and Liquid Crystal Handbook (published by Maruzen Company, Limited in 2000) on pages 330 to 333 , a compound in which at least one (preferably three or more) of the terminals is an epoxy group.

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

Moreover, the compound represented by formula (D16) is also preferable as a discotic compound from a viewpoint of the thermal conductivity of a thermally conductive material being more excellent.

[chemical formula 12]

In formula (D16), A ^2X , A ^3X and A ^4X each independently represent -CH= or -N=. Among them, A ^2X , A ^3X and A ^4X are all -CH= or all -N= are preferred. That is, it is preferable that the 6-membered ring including A ^2X , A ^3X and A ^4X is a benzene ring or a tricyclic ring. R ^17X , R ^18X and R ^19X each independently represent *-X ^211X -(Z ^21X -X ^212X ) _n21X -L ^21X -Q. * Indicates the bonding position to the central ring. X ^211X and X ^212X independently represent 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 represent a 5-membered or 6-membered aromatic ring group or a 5-membered or 6-membered non-aromatic ring group. L ^21X represents a single bond or a divalent linking group. The meaning of Q is the same as that of Q in the formulas (D1) to (D15), and the preferable range is also the same. In the formula (D16), at least one (preferably all) of Q among the plural Qs represents an epoxy group. n21X represents an integer of 0-3. When n21X is 2 or more, a plurality of (Z ^21X -X ^212X ) that exist may be the same or different.

As the compound represented by formula (D16), a compound represented by formula (XII) is preferable.

[chemical formula 13]

In formula (XII), A ² , A ³ and A ⁴ each independently represent -CH= or -N=. Among them, A ² , A ³ and A ⁴ are all -CH= or all are -N=, which is preferred. That is, it is preferable that the 6-membered ring including A ² , A ³ and A ⁴ is a benzene ring or a tricyclic ring.

R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent *-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. Two or more of R ¹⁷ , R ¹⁸ and R ¹⁹ are *-X ²¹¹ -(Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ²¹ . From the standpoint of better thermal conductivity of the thermally conductive material, R ¹⁷ , R ¹⁸ and R ¹⁹ are all *-X ²¹¹ -(Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ²¹ are preferred. In addition, it is preferable that R ¹⁷ , R ¹⁸ and R ¹⁹ are all the same.

X ²¹¹ , X ²¹² , X ²²¹ and X ²²² each independently represent 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 preferably each independently a single bond, -NH-, -O-, or -CO-O-.

Z ²¹ and Z ²² each independently represent a 5-membered or 6-membered aromatic ring group or a 5-membered or 6-membered non-aromatic ring group. For example, a phenyl ring group (1,4-phenylene group, 1,3-phenylene group, etc.) and an aromatic heterocyclic group are mentioned.

The above-mentioned aromatic ring group and the above-mentioned non-aromatic ring group may have a substituent. When having a substituent, the number of substituents is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1. The substitution position of the substituent is not particularly limited. As the substituent, a halogen atom or a methyl group is preferable. It is also preferable that the above-mentioned aromatic ring group and the above-mentioned non-aromatic ring group are unsubstituted. Also, as a substituent, it may further have a group represented by "-X ²¹² -L ²¹ -P ²¹ ".

Examples of the aromatic heterocyclic group include the following aromatic heterocyclic groups.

[chemical formula 14]

In the formula, * represents the site bonded to ^X211 or ^X221 . ** Indicates the site bonded to X ²¹² or X ²²² . A ⁴¹ and A ⁴² each independently represent a methine group or a nitrogen atom. X ⁴ represents an oxygen atom, a sulfur atom or an imine group. It is preferable that at least one of A ⁴¹ and A ⁴² is a nitrogen atom, and it is more preferable that both are a nitrogen atom. Also, X ⁴ is preferably an oxygen atom.

When n21 and n22 to be described later are 2 or more, there are a plurality of (Z ²¹ -X ²¹² ) and (Z ²² -X ²²² ) which may be the same or different.

L ²¹ each independently represent a single bond or a divalent linking group, and have the same meaning as L ¹¹ in the formula (XI) described above. As L ²¹ , -O-, -CO-O-, -S-, -NH-, alkylene group (preferably 1-10 carbon atoms, more preferably 1-8 carbon atoms, still more preferably 1-7 carbon atoms) ), an aryl group (preferably 6-20 carbons, more preferably 6-14, further preferably 6-10.) or a group consisting of these combinations is preferred.

When n22 described later is 1 or more, examples of -X ²¹² -L ²¹ - include examples L101 to L143 of L in the above formulas (D1) to (D15) in the same manner. Among them, the bonds on the left side of L101 to L143 are bonded to the central structure (hereinafter, also simply referred to as “central ring”) side of the compound, and the bonds on the right side are bonded to P ²¹ .

P ²¹ represents an epoxy group. The said epoxy group may have a substituent, and may not have a substituent.

Y and ²² each independently represent a hydrogen atom, a straight chain having 1 to 20 carbons, a branched chain having 1 to 20 carbons, a cyclic alkyl group having 1 to 20 carbons, or a straight chain having 1 to 20 carbons One or two or more methylene groups in a branched-chain or cyclic alkyl group with 1 to 20 carbons are replaced by -O-, -S-, -NH-, -N( A group substituted by CH ₃ )-, -CO- or -CO-O- has the same meaning as Y ¹² in formula (XI), and the preferred range is also the same.

n21 and n22 each independently represent the integer of 0-3, and the integer of 1-3 is preferable from a viewpoint of being more excellent in thermal conductivity. Among them, when A ² , A ³ and A ⁴ are all -CH=, it is more preferable that n21 and n22 are independently integers of 2 to 3, and when A ² , A ³ and A ⁴ are all -N= In this case, it is more preferable that n21 and n22 are each independently 1.

Preferable examples of discotic compounds include the following compounds.

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

In addition, in the following structural formulas, R represents -X ²¹² -L ²¹ -P ²¹ .

[chemical formula 21]

[chemical formula 22]

For details and specific examples of the compound represented by formula (XII), see the compounds described in paragraphs [0013] to [0077] of JP-A-2010-244038, wherein at least one of the terminals ( Preferably 3 or more) as the compound of the epoxy group, and this content is incorporated into this specification.

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

In addition, the discotic compound is also preferably a compound having a hydrogen-bonding functional group from the viewpoint of reducing the electron density to enhance stacking and easily forming columnar aggregates. Examples of the hydrogen-bonding functional group include -O-CO-NH-, -CO-NH-, -NH-CO-NH-, and -NH-CO-S-.

(Other Epoxy Compounds) The epoxy compound may contain other epoxy compounds in addition to the above-mentioned epoxy compounds. As other epoxy compounds, for example, in the compound represented by formula (Z), the compound represented by formula (Z1) or the compound represented by formula (Z2) described above, it is also possible to use Epoxy compounds. The epoxy group-containing group is a group that is an epoxy group itself or is a valent group partially containing an epoxy group. The valent group partly containing the said epoxy group is a group which has 1 or more (preferably 1-8) epoxy groups in the whole group. It is preferable that the valent group partly including the above epoxy group is a group represented by "-(divalent hydrocarbon group) _M1 -(-O-divalent hydrocarbon group-) _M2 -epoxy group". In the above groups, M1 represents 0 or 1. M2 represents an integer of 1 or more (preferably 1 to 10). Examples of divalent hydrocarbon groups in the above groups include alkylene groups (preferably having 1 to 6 carbon atoms), alkenylene groups (-CH=CH-, etc., preferably having 2 to 6 carbon atoms), Alkynylene group (-C≡C-, etc., preferably having 2 to 6 carbon atoms), arylylene group (phenylene group, etc., preferably having 6 to 15 carbon atoms), and a combination thereof. The above-mentioned divalent hydrocarbon group may or may not have a substituent, and the above-mentioned divalent hydrocarbon group may further have an epoxy-containing group as a substituent. A plurality of the above-mentioned divalent hydrocarbon groups may be present and may be the same or different.

As other epoxy compounds, for example, epoxy compounds represented by formula (DN) can also be mentioned.

[chemical formula 23]

In the 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. As a divalent linking group, -O-, -CO-O-, -S-, alkylene (preferably 1 to 10 carbons), arylylene (preferably 6 to 20 carbons) or the Groups formed by combining such groups are preferred, alkylene groups are more preferred, and methylene groups are further preferred.

As another epoxy compound, the epoxy compound represented by formula (E2) is also mentioned. (V-) _4-U C (-W) _U (E2)

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

In formula (E2), U represents an integer of 3 or 4. In the formula (E2), "U" in "4-U" representing the number of V and "U" representing the number of W represent the same value. That is, the formula (E2) is "VC(-W) ₃ " or "C(-W) ₄ ".

In formula (E2), V represents a hydrogen atom or a substituent not having an epoxy group. The above-mentioned substituent not having an epoxy group is a substituent other than an epoxy group, and is a substituent not including an epoxy group as a part of the substituent. As the substituent not having the above-mentioned epoxy group, for example, a group selected from the substituent group Y and a group other than an epoxy group and a group partially containing an epoxy group can be mentioned. The above-mentioned substituent not having an epoxy group is preferably an alkyl group, and more preferably a straight-chain or branched-chain alkyl group. It is preferable that the carbon number of the said alkyl group is 1-5.

In the formula (E2), W represents an epoxy group-containing group. The epoxy group-containing group is a group that is an epoxy group itself or is a valent group partially containing an epoxy group. The valent group partly containing the said epoxy group is a group which has 1 or more (preferably 1-8) epoxy groups in the whole group. It is preferable that the valent group partly including the above epoxy group is a group represented by "-(divalent hydrocarbon group) _M1 -(-O-divalent hydrocarbon group-) _M2 -epoxy group". In the above groups, M1 represents 0 or 1. M2 represents an integer of 1 or more (preferably 1 to 10). Examples of divalent hydrocarbon groups in the above groups include alkylene groups (preferably having 1 to 6 carbon atoms), alkenylene groups (-CH=CH-, etc., preferably having 2 to 6 carbon atoms), Alkynylene group (-C≡C-, etc., preferably having 2 to 6 carbon atoms), arylylene group (phenylene group, etc., preferably having 6 to 15 carbon atoms), and a combination thereof. The above-mentioned divalent hydrocarbon group may or may not have a substituent, and the above-mentioned divalent hydrocarbon group may further have an epoxy-containing group as a substituent. A plurality of the above-mentioned divalent hydrocarbon groups may be present and may be the same or different. In the formula (E2), there are a plurality of Ws which may be the same or different.

As another epoxy compound, the compound which epoxy group condensed ring can also be mentioned, for example. Such a compound includes, for example, 3,4:8,9-diepoxybicyclo[4.3.0]nonane.

Examples of other epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds such as bisphenol A, F, S, and AD as glycidyl ethers. Compounds and bisphenol AD-type epoxy compounds; hydrogen-added bisphenol A-type epoxy compounds and hydrogen-added bisphenol AD-type epoxy compounds; phenol novolac-type glycidyl ethers (phenol novolac-type ring Oxygen compounds), cresol novolak type glycidyl ether (cresol novolak type epoxy compound) and bisphenol A novolak type glycidyl ether; dicyclopentadiene type glycidyl ether Ethers (dicyclopentadiene-type epoxy compounds); dihydroxypentadiene-type epoxypropyl ethers (dihydroxypentadiene-type epoxy compounds); dihydroxybenzenes such as resorcinol, etc. Polyhydroxybenzene type glycidyl ether (polyhydroxybenzene type epoxy compound) such as base ether; benzene polycarboxylate type glycidyl ester (benzene polycarboxylate type epoxy compound); triphenolmethane type ring Oxygen compounds; phenoxy resins; and acrylic resins having epoxy groups in side chains. One or more of the glycidyl ether groups and/or glycidyl ester groups in the above-mentioned compounds can be substituted with a diecidylamino group or a dielycidylamino alkylene group ( Diglycidylaminomethylene, etc.) compounds are used as epoxy compounds. 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-mentioned compounds may have Substituents other than diglycidylaminoalkylene.

An epoxy compound may be used individually by 1 type, and may use 2 or more types. The content of the epoxy compound is preferably 1.0 to 90.0% by mass, more preferably 3.0 to 50.0% by mass, further preferably 5.0 to 40.0% by mass, and particularly preferably 5.0 to 10.0% by mass, based on the total solid content of the composition.

[Relationship between phenolic compounds and epoxy compounds] It is preferable to satisfy at least one of the conditions that the phenol compound contains a phenolic compound having a three-skeleton (requirement 1) and the epoxy compound contains an epoxy compound having a three-skeleton (requirement 2), and the phenol compound contains a phenol having a three-skeleton Compound (requirement 1) and epoxy compound containing epoxy compound (requirement 2) with three-skeleton is more preferable, satisfying phenolic compound containing phenol compound with three-skeleton (requirement 1) and not satisfying ring It is still more preferable that the oxygen compound contains an epoxy compound (requirement 2) having a three-skeleton. The composition may satisfy only requirement 1, may satisfy only requirement 2, or may satisfy both requirement 1 and requirement 2.

The phenolic compound and the epoxy compound "having a tri-skeleton skeleton" means having one or more (for example, 1 to 5) tri-skeletal ring groups in the compound. Examples of the phenol compound having a three-skeleton structure include the compound represented by the formula (Z), the compound represented by the formula (Z1), and the compound represented by the formula (Z2). As an epoxy compound having a three-skeleton, for example, a compound in which A ^2X , A ^3X and A ^4X are all in the form of -N= among the compounds represented by the above-mentioned formula (D16), represented by the formula (XII) Among the compounds, A ² , A ³ and A ⁴ are all compounds in the form of -N=. In formula (Z), the phenolic hydroxyl group is replaced by a compound containing an epoxy group. In formula (Z1), the phenolic hydroxyl group is replaced by In the epoxy-group-containing compound and the formula (Z2), the phenolic hydroxyl group is replaced by an epoxy-group-containing compound.

When the phenolic compound contains a phenolic compound having a three-skeleton structure (condition 1 is satisfied), the content of the phenol compound having a three-skeleton structure is more than 0% by mass and not more than 100% by mass relative to the total mass of the phenolic compound. Preferably, 30-100 mass % is more preferable, 60-100 mass % is further more preferable, and 90-100 mass % is especially preferable. In addition, when the composition contains an epoxy compound, and the epoxy compound includes an epoxy compound with a three-skeleton skeleton (condition 2 is satisfied), the content of the epoxy compound with a three-skeleton skeleton is within the above-mentioned preferred range It is also better to be outside the range. When the epoxy compound contains an epoxy compound having a three-skeleton skeleton (condition 2 is satisfied), the content of the epoxy compound having a three-skeleton skeleton is more than 0% by mass and 100% by mass relative to the total mass of the epoxy compound % or less is preferable, 30-100 mass % is more preferable, 60-100 mass % is still more preferable, and 90-100 mass % is especially preferable. In addition, when the phenolic compound contains a phenol compound having a three-skeleton structure (when Requirement 1 is satisfied), it is also preferable that the content of the phenol compound having a three-skeleton structure is outside the above-mentioned preferred range.

It is also preferable that at least a part of the phenolic compound and the epoxy compound is not a compound having a triple skeleton. All or part of the phenolic compound does not have to be a compound having a three-skeleton structure, and all or a part of the epoxy compound does not have to be a compound having a three-skeleton structure. From the viewpoint of adjusting the crosslink density to further enhance the effect of the present invention, the total content of the phenolic compound having a three-skeleton skeleton and the epoxy compound having a three-skeleton skeleton is more than the total content of all phenolic compounds and all epoxy compounds. 0 mass % to less than 100 mass % is preferable, 1-90 mass % is more preferable, 5-80 mass % is still more preferable.

The total content of the epoxy compound and the phenol compound is preferably 3 to 90% by mass, more preferably 5 to 50% by mass, and still more preferably 7 to 40% by mass, based on the total solid content of the composition.

The ratio of the number of epoxy groups contained in the epoxy compound to the number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenolic compound (number of epoxy groups/number of hydroxyl groups) is 3/97 to 97/ 3 is preferred, 30/70 to 70/30 is more preferred, 40/60 to 60/40 is further preferred, and 45/55 to 55/45 is particularly preferred. That is, it is preferable that the ratio of the content of the phenol compound and the epoxy compound is such that the above-mentioned "the number of epoxy groups/the number of phenolic hydroxyl groups" is within the above-mentioned range.

The equivalent ratio of epoxy groups to active hydrogens (the active hydrogens from phenolic hydroxyl groups or other active hydrogen-containing compounds) of epoxy compounds (the number of epoxy groups/the number of active hydrogens) 3/97 to 97/3 is preferable, 30/70 to 70/30 is more preferable, 40/60 to 60/40 is still more preferable, and 45/55 to 55/45 is particularly preferable.

[Aggregated Boron Nitride] The composition of the present invention contains aggregated boron nitride. Aggregated boron nitride is secondary aggregated particles formed by aggregating 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, more preferably 40 μm or more. The upper limit is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, and particularly preferably 100 μm or less. "Particle diameter" means the average particle diameter of particles measured by the following method. The average particle size can be measured using a scanning electron microscope (Scanning Electron Microscope, SEM) or a laser diffraction particle size distribution measuring device. As a scanning electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. The maximum length (Dmax: the maximum length between two points on the contour of the particle image) and the vertical length of the maximum length (DV-max: parallel to the maximum length) of the particle image obtained using a scanning electron microscope When the image is clamped by two straight lines, the shortest length between the two straight lines is vertically connected) for measurement, and the geometric mean value (Dmax×DV-max) ^1/2 is taken as the particle size. The particle diameters of 100 particles are measured by this method, and the arithmetic mean thereof is taken as the average particle diameter of the particles. The condensed boron nitride preferably includes surface-modified condensed boron nitride described later.

Agglomerated boron nitride can be surface treated. In addition, surface treatment means a treatment different from surface modification using a surface modifying agent described later. It is presumed that by performing these treatments, functional groups are introduced into the surface of the aggregated boron nitride, and the aggregated boron nitride easily interacts with phenolic compounds, epoxy compounds, and/or surface modifiers described later, and the resulting The thermal conductivity and peak strength of the formed thermal conductive material are further improved. Examples of surface treatment include plasma treatment (vacuum plasma treatment, atmospheric pressure plasma treatment, hydroplasma treatment, etc.), ultraviolet irradiation treatment, corona treatment, electron beam irradiation treatment, ozone treatment, firing treatment, flame treatment, etc. treatment and oxidant treatment. The oxidizing agent treatment may be performed under acidic conditions, or may be performed under alkaline conditions (pH 12 or higher, etc.).

Agglomerated boron nitride may be used alone or in combination of two or more. The content of the aggregated boron nitride is preferably at least 20% by mass, more preferably at least 50% by mass, and still more preferably at least 60% by mass, based on the total solid content of the composition. The upper limit is preferably less than 100 mass % with respect to the total solid content of the composition, more preferably 95 mass % or less, still more preferably 80 mass % or less.

〔Inorganic substance X〕 The composition of the present invention contains an inorganic substance X. The inorganic substance X refers to at least one selected from the group consisting of alumina and silica. The average particle size of inorganic substance X (average particle size of alumina or average particle size of silica) is 0.30 μm or less, preferably less than 0.30 μm, more preferably 0.25 μm or less, more preferably 0.20 μm or less, 0.15 Below μm is particularly preferred. The lower limit is preferably at least 0.001 μm, more preferably at least 0.01 μm. The meaning of the above-mentioned particle diameter is the same as that of the above-mentioned condensed boron nitride, and the measurement method is also the same. As the inorganic substance X, alumina or silica is preferable, and surface-modified alumina described later or surface-modified silica described later is more preferable.

(alumina) The shape of alumina may be granular or plate-like. Examples of the particle shape include a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a scale shape, an aggregated shape, and an indeterminate shape. Alumina may also be alumina produced by oxidizing aluminum metal prepared as a non-oxide under ambient conditions. Alumina preferably includes surface-modified alumina described later.

(silicon dioxide) The shape of silicon dioxide may be granular or plate-like. The particle shape includes, for example, a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a scaly shape, an aggregated shape, and an indeterminate shape, and a spherical shape is preferable. Silica preferably includes surface-modified silica described later.

〔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 substances are not particularly limited as long as they are substances other than the specific inorganic substances described above. As another inorganic substance, a well-known inorganic substance is mentioned, for example, and the inorganic substance used as the inorganic filler of a thermally-conductive material beforehand can also be used. In other words, other inorganic substances may also contain at least one selected from the group consisting of agglomerated boron nitride with an average particle size of less than 20 μm, alumina with an average particle size of more than 0.30 μm, and silicon dioxide with an average particle size of more than 0.30 μm. . Among them, as the other inorganic substances, it is preferable to contain at least one selected from the group consisting of alumina having an average particle diameter of more than 0.30 μm and silica having an average particle diameter of more than 0.30 μm.

Examples of other inorganic substances include inorganic nitrides and inorganic oxides. The shape of other inorganic substances may be particle, film or plate. Examples of the particle shape include a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a scale shape, an aggregated shape, and an indeterminate shape. Other inorganic substances may include other surface-modifying inorganic substances described later.

Examples of inorganic nitrides include boron nitride (BN), carbon nitride (C ₃ N ₄ ), silicon nitride (Si ₃ N ₄ ), gallium nitride (GaN), and indium nitride (InN). , aluminum nitride (AlN), chromium nitride (Cr ₂ N), copper nitride (Cu ₃ N), iron nitride (Fe ₄ N), iron nitride (Fe ₃ N), lanthanum nitride (LaN) , lithium nitride (Li ₃ N), magnesium nitride (Mg ₃ N ₂ ), molybdenum nitride (Mo ₂ N), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN), Tungsten nitride (W ₂ N), tungsten dinitride (WN ₂ ), yttrium nitride (YN) and zirconium nitride (ZrN).

Examples of inorganic oxides include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), iron oxide (Fe ₂ O ₃ , FeO, Fe ₃ O ₄ ), copper oxide (CuO, Cu ₂ O), Zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ) , tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), germanium oxide (GeO ₂ , GeO), lanthanum oxide (La ₂ O ₃ ) and ruthenium oxide (RuO ₂ ). It is also preferable that the inorganic oxide is different from the inorganic ion-scavenging agent described later. The inorganic oxide may be an oxide produced by oxidizing a metal prepared as a non-oxide under ambient conditions or the like. The other inorganic substances may be used alone or in combination of two or more.

The inorganic substance X may be used alone or in combination of two or more. The content of the inorganic substance X is preferably at least 0.1% by mass, more preferably at least 1% by mass, and still more preferably at least 2% by mass, 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, still more preferably 20% by mass or less, particularly preferably 15% by mass or less, most preferably 8% by mass or less, relative to the total solid content of the composition. .

The mass ratio of the content of condensed boron nitride to the content of inorganic substance X (content of condensed boron nitride/content of inorganic substance X) is preferably 0.6 to 99.0, more preferably 1.0 to 30.0, and more preferably 3.0 to 25.0. Good, 5.0-25.0 is very good, 7.0-25.0 is the best.

The content of other inorganic substances is preferably at least 1% by mass, more preferably at least 3% by mass, based on the total solid content of the composition. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total solid content of the composition. The mass ratio of the content of condensed boron nitride to the total content of other inorganic substances and inorganic substances X (content of condensed boron nitride/total content of other inorganic substances and inorganic substances X) is preferably 1.0 to 50.0, more preferably 1.0 to 30.0 Good, and 1.0 to 10.0 is still more preferable.

〔Surface modification agent, surface modification condensed boron nitride and surface modification inorganic substance X〕 The composition of the present invention may further contain a surface modifier as a component other than the above components. The surface modifier is a component for surface modification of the above-mentioned condensed boron nitride, inorganic substance X and other inorganic substances. Surface modification refers to a state in which an organic substance is adsorbed on at least a part of the surface of a specific inorganic substance. The form of adsorption is not particularly limited, as long as it is in a bonded state. That is, surface modification also includes a state in which an organic group obtained by detaching a part of an organic substance is bonded to the surface of a specific inorganic substance. The bond may be any of covalent bond, coordinate bond, ionic bond, hydrogen bond, van der Waals bond (van der Waals bond) and metallic bond. Surface modification may be performed to form a monomolecular film on at least a portion of the surface. Monomolecular film is a monolayer film formed by chemical adsorption of organic molecules, which is called Self-Assembled Mono Layer (SAM). In addition, in the present specification, surface modification may be performed on only a part of the surface of the inorganic substance, or may be performed on the entire surface of the inorganic substance.

(Specific inorganic substances for surface modification) The surface-modified specific inorganic substance refers to a specific inorganic substance surface-modified with a surface modifying agent (hereinafter, also referred to as "surface-modified specific inorganic substance"). That is, the surface-modifying inorganic substance is a material including a specific inorganic substance and a surface modifier adsorbed on the surface of the above-mentioned specific inorganic substance. That is, the specific inorganic substance can constitute a surface-modified specific inorganic substance together with a surface modifying agent adsorbed on the surface of the specific inorganic substance. Also, in the present invention, since the composition contains the specific inorganic substance for surface modification, the composition may contain the specific inorganic substance and the surface modifying agent. Part or all of the specific inorganic substance in the composition may constitute the surface-modifying specific inorganic substance together with the surface modifier. For example, the specific inorganic substance that does not participate in the composition of the specific inorganic substance for surface modification may exist in the composition while constituting a part of the specific inorganic substance for surface modification. A part or all of the surface modifying agent in the composition may constitute the specific inorganic substance for surface modification together with the specific inorganic substance. For example, a surface-modifying agent may be present in the composition while constituting a part of the surface-modifying specific inorganic substance and not participating in the constitution of the specific surface-modifying inorganic substance. The surface-modified specific inorganic substance can be formed, for example, by bringing the specific inorganic substance into contact with a surface modifier. Specifically, the specific inorganic substance for surface modification can be formed in the composition during the process of mixing the specific inorganic substance, a surface modifier, and other components constituting the composition of the present invention to produce the composition of the present invention. In addition, it is possible to prepare a mixed liquid containing a surface-modified specific inorganic substance by mixing a specific inorganic substance and a surface modifying agent in a solvent, and separate the surface-modified specific inorganic substance from the above-mentioned mixed liquid by a method such as filtration to obtain the separated surface-modified specific inorganic substance. Inorganic matter. The composition of the present invention can be prepared using the isolated surface-modifying specific inorganic substance.

(surface modifier) Examples of surface modifiers include known surface modifiers such as carboxylic acids such as long-chain alkyl fatty acids, organic phosphonic acids, organic phosphoric acid esters, and organosilane molecules (silane coupling agents), JP-A-2009-502529, A surface modifier described in Japanese Patent Application Laid-Open No. 2001-192500 and Japanese Patent No. 4694929.

As said silane coupling agent, the compound which has the hydrolyzable group directly bonded to Si atom is mentioned, for example. Examples of the hydrolyzable group include alkoxy groups (preferably having 1 to 10 carbon atoms) and halogen atoms such as chlorine atoms. The number of hydrolyzable groups directly bonded to Si atoms that the silane coupling agent has is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit is preferably 10000. It is also preferable that the silane coupling agent has a reactive group. Examples of the above reactive group include epoxy group, oxetanyl group, vinyl group, (meth)acryl group, styryl group, amine group, isocyanate group, mercapto group and acid anhydride group. The number of reactive groups that the silane coupling agent has is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit is preferably 10000 or less. As the silane coupling agent, for example, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane and 3-urea Propyltriethoxysilane.

When the composition of the present invention contains a surface modifying agent, the specific inorganic substance for surface modification can be prepared in advance and used as a part of the raw materials of the composition. That is, it is possible to mix the prefabricated surface-modifying inorganic substance with other various components of the composition, thereby introducing all or part of the surface modifying agent and the specific inorganic substance into the form contained in the prefabricated surface-modifying inorganic substance. in the composition. In addition, other than the surface modifying agent and the inorganic substance introduced in the form contained in the surface-modifying specific inorganic substance, the surface modifying agent and/or the specific inorganic substance in the state where the surface-modifying inorganic substance is not formed may be mixed with other components of the composition , and introduce all or part of the surface modifier and/or specific inorganic substances into the composition. In this case, it is also preferable that the surface modifier is adsorbed on the surface of the specific inorganic substance during the mixing process, and that the surface-modified specific inorganic substance is formed in the composition. Also, in this case, a part of the surface modifier may exist in the composition in a state that does not contribute to the formation of the specific inorganic substance for surface modification. In addition, although the aspect of the specific inorganic substance was described above, the specific inorganic substance may be replaced with another inorganic substance in the above description. That is, other inorganic substances can also be surface-modified according to the above-mentioned aspects.

A surface modifier may be used individually by 1 type, and may use 2 or more types. The content of the surface modifier is preferably 0.005 to 5% by mass, more preferably 0.05 to 3% by mass, based on the total solid content of the composition. The content of the surface modifier is preferably 0.01 to 10% by mass, more preferably 0.10 to 5% by mass, based on the total mass of all inorganic substances. In addition, all inorganic substances refer 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 0.00001-0.5, more preferably 0.0001-0.1. The content of the specific surface-modifying inorganic substance is preferably 20% by mass or more, more preferably 50% by mass or more, still 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 at most 95% by mass, and still more preferably at most 85% by mass.

〔Acid anhydride〕 The composition may contain an acid anhydride. An acid anhydride is a compound having one or more acid anhydride groups (groups represented by -CO-O-CO-).

The number of acid anhydride groups having an acid anhydride is 1 or more, preferably 2 or more, more preferably 3 or more. As an upper limit of the said number, it is 1000 or less, for example. 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 2,000 or more, and still more preferably 6,000 or more. The upper limit of the molecular weight is preferably at most 100,000, more preferably at most 30,000, and still more preferably at most 17,000. The acid anhydride may be a low-molecular compound or a high-molecular compound. Examples of acid anhydrides of low molecular weight compounds include maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. In the acid anhydride which is a polymer compound, the acid anhydride group may exist embedded in the main chain, or may exist in the side chain. In addition, for example, when the above-mentioned polymer compound has a maleic acid-based repeating unit, the acid anhydride group contained in the above-mentioned repeating unit is embedded in the main chain.

The acid anhydride group may form a ring together with atoms other than the atoms included in the acid anhydride group, or may not form a ring. Among them, it is preferable that the acid anhydride group forms a ring. The aforementioned ring may be monocyclic or polycyclic, and the number of ring member atoms is, for example, 5-15. For example, it is preferable that the acid anhydride has a group represented by the formula (A).

[chemical formula 24]

In formula (A), * ^S and * ^T represent the bonding position with a carbon atom. Among them, the carbon atom bonded by * ^S and the carbon atom bonded by * ^T are adjacent atoms directly bonded to each other. That is, the group represented by the formula (A), the carbon atoms bonded by * ^S and the carbon atoms bonded by * ^T jointly form a 5-membered ring. Also, the type of bond between the carbon atom bonded by * ^S and the carbon atom bonded by * ^T is not limited, for example, it may be a single bond (Single Bond) or a double bond. Also, the group represented by the formula (A), the carbon atom bonded by * ^S and the carbon atom bonded by * ^T can be condensed into an aromatic ring (benzene ring, etc.) with a 5-membered ring, so that The carbon atom bonded by * ^S and the carbon atom bonded by * ^T become adjacent ring member atoms in the same aromatic ring. The above-mentioned aromatic ring may be monocyclic or polycyclic, may or may not have heteroatoms, and the number of ring members is, for example, 5-15.

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

[chemical formula 25]

In the formula (B), one or two of R ^A1 to R ^A4 represent bonding positions, and the others each independently represent a hydrogen atom or a substituent. When two of R ^A1 to R ^A4 are binding positions, for example, R ^A1 and R ^A2 may be binding positions, or any one of R ^A1 and R ^A2 and R ^A3 and R ^A4 may be used. Any one of them becomes the bonding position respectively. Examples of substituents that may be represented by R ^A1 to R ^A4 include groups selected from the substituent group Y described above. Moreover, the total number of atoms other than a hydrogen atom in the said substituent is 1-20, for example.

In formula (C), R ^B1 and R ^B2 each independently represent a hydrogen atom, a substituent, or a bonding position. Wherein, one or both of R ^B1 and R ^B2 are bonding positions. Examples of substituents that may be represented by R ^B1 and R ^B2 include groups selected from the substituent group Y described above. Moreover, the total number of atoms other than a hydrogen atom in the said substituent is 1-20, for example.

In the formula (D), * represents a bonding position. The aforementioned bonding position 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 above-mentioned aromatic ring may be monocyclic or polycyclic, may or may not have heteroatoms, and the number of ring members is, for example, 5-15. Among them, the above-mentioned aromatic ring is preferably a benzene ring. In the formula (DN), n represents an integer of 0 or more, preferably an integer of 0-2, and more preferably 0 or 1. In formula (D), there are (n+1) 5-membered rings having a group represented by -CO-O-CO-, and (n+1) 5-membered rings are condensed into an aromatic ring represented by Ar. For example, when n is 0, the group represented by the formula (D) is a group represented by the following formula (D0), and when n is 1, the group represented by the formula (D) is A group represented by the following formula (D1). The meanings of *, m, and Ar in the following formula (D0) and the following formula (D1) are the same as those of *, m, and Ar in the formula (D).

[chemical formula 26]

The number of groups represented by the formula (A) having an acid anhydride is preferably 1 or more, more preferably 2 or more. As an upper limit of the said number, it is 1000 or less, for example. Also, the number of groups selected from the group including the group represented by the formula (B) and the group represented by the formula (C) having an acid anhydride is preferably 1 or more, more preferably 2 or more. Excellent, 3 or more are further preferred. As an upper limit of the said number, it is 1000 or less, for example. The number of groups represented by the formula (D) having an acid anhydride is preferably one or more. As an upper limit of the said number, it is 1000 or less, for example.

Among them, it is preferable that the acid anhydride is a polymer compound. Also, the acid anhydride preferably has a repeating unit represented by the following formula (X), and more preferably has a repeating unit represented by the formula (X) and a repeating unit represented by the formula (Y).

[chemical formula 27]

In formula ( ^Y ), RY 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. As a hetero atom in the said aromatic heterocyclic group, an oxygen atom, a sulfur atom, and a nitrogen atom are mentioned, for example. The above aromatic ring group preferably has 5 to 15 ring member atoms. As a substituent which the said aromatic ring group may have, the group selected from the said substituent group Y is mentioned, for example. Moreover, the total number of atoms other than a hydrogen atom in the said substituent is 1-20, for example. The number of substituents which the said aromatic ring group may have is 0-5, for example. Among them, ^RY is preferably an unsubstituted phenyl ring group. The repeating unit represented by formula (Y) may be used alone or in combination of two or more.

When the acid anhydride has a repeating unit represented by formula (X), the other content is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass relative to all the repeating units of the acid anhydride for further improvement. When the acid anhydride has a repeating unit represented by the formula (Y), the other content is preferably 10 to 90 mass % with respect to all the repeating units of the acid anhydride.

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

[chemical formula 28]

In formula (Z), R ^Z1 to R ^Z4 each independently represent a hydrogen atom or a substituent. Among R ^Z1 to R ^Z4 , 0 to 2 are preferably the above substituents. As said substituent, the group selected from the said substituent group Y is mentioned, for example. Moreover, the total number of atoms other than a hydrogen atom in the said substituent is 1-20, for example. Among them, as the above-mentioned substituents, each independently -COOH, -O-CO-R or linear or branched alkyl group is preferable. R in -O-CO-R represents an organic group, and a linear or branched alkyl group is preferred, and a linear or branched alkyl group having 1 to 4 carbon atoms is more preferred. As the repeating unit represented by the formula (Z), for example, repeating units in which R ^Z1 to R ^Z4 are hydrogen atoms, R ^Z1 and R ^Z3 are hydrogen atoms, R ^Z2 and R ^Z4 are -COOH repeating units, and R ^Z1 to R ^Z3 are hydrogen atoms and R ^Z4 is a repeating unit of -O-CO-R. However, the repeating unit represented by formula (Z) is a repeating unit different from the repeating unit represented by formula (Y). Specifically, the form in which three of R ^Z1 to R ^Z4 are hydrogen atoms and one is an aromatic ring group is not included in the repeating unit represented by formula (Z). 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 the formula (Z), the other content is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass relative to all the repeating units of the acid anhydride. Further better.

As the acid anhydride, a commercially available item can be used. Examples of commercially available acid anhydrides include SMA series manufactured by TOMOE ENGINEERING CO., LTD. (XIRAN series manufactured by Polyscope Polymers B.V.), OREVAC T series manufactured by Arkema S.A., and ARASTAR manufactured by Arakawa Chemical Industries, Ltd. series.

Acid anhydride may use only 1 type, and may use 2 or more types. 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 still 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 still more preferably from 5 to 60% by mass, based on the total content of the epoxy compound and the phenol compound.

[Maleimide compound] From the viewpoint of excellent heat resistance (glass transition temperature Tg) of the heat conductive material, it is preferable that the composition of the present invention further contains a maleimide compound. It is considered that, when the composition contains a maleimide compound, the maleimide compound and the phenolic compound undergo an addition reaction and/or the polymer structure produced by the above addition reaction is compared with that produced by the The polymer structure formed by other components in the composition forms such as an interpenetrating polymer network, thereby increasing the density of the polymer structure of the thermally conductive material, and further improving the thermal conductivity and heat resistance of the thermally conductive material (Tg ). In addition, since a denser polymer structure is formed in the heat-conducting material, water becomes less likely to penetrate into the heat-conducting material and the hygroscopicity is also suppressed, and when the heat-conducting material is exposed to high temperature, thermal decomposition of constituent components can also be suppressed. Generates volatile low molecules in thermally conductive materials. As a result, it is considered that even when the heat conduction material is exposed to high temperature, it is possible to suppress the vaporization of volatile components from the heat conduction material to reduce the adhesiveness, thereby further improving the solder heat resistance of the heat conduction material.

The maleimide compound refers to a maleimide compound having one or more maleimide groups. Among them, as the maleimide compound, a maleimide compound having 1 or 2 maleimide groups is preferable, and a maleimide compound having 2 maleimide groups is preferable. The maleimide compound (bismaleimide compound) is more preferable.

The number of the maleimide groups which the maleimide compound has is 1 or more, Preferably it is 1-100, More preferably, it is 2-10, More preferably, it is 2. The maleimide compound may be either a high-molecular compound or a low-molecular compound. The molecular weight of the maleimide compound is preferably from 100 to 3,000, more preferably from 200 to 2,000, and still more preferably from 300 to 1,000.

As the maleimide group which the maleimide compound has, a group represented by the formula (M) is preferable.

[chemical formula 29]

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

X and Y each independently represent a hydrogen atom or a substituent. Examples of the above-mentioned substituent include groups exemplified in the substituent group Y described above. Hydrogen atoms are preferred as X and Y.

It is also preferable that the maleimide compound is a compound having one or more (preferably 1 to 10) aromatic ring groups (phenyl ring groups, etc.). The maleimide compound is preferably a compound represented by the following formula (1).

[chemical formula 30]

In formula (1), m represents 0 or 1. As m, 1 is preferable. n represents 0 or 1. As n, 1 is preferable.

In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. As the above-mentioned substituent, an alkyl group is preferable. The above-mentioned alkyl group may be linear or branched, and the number of carbon atoms in the above-mentioned alkyl group is preferably 1 to 10. In the case where R ¹ and/or R ² represent a substituent, it is also preferred that R ¹ and/or R ² exist at a position adjacent to the maleimide group on the phenyl ring group. When both R ¹ and R ² represent substituents, R ¹ and R ² are preferably different substituents, R ¹ represents methyl, and R ² represents ethyl.

In formula (1), L ¹ represents a divalent linking group. Examples of the divalent linking group include ether group (-O-), carbonyl group (-CO-), ester group (-COO-), thioether group (-S-), -SO ₂ -, - NR- (R is a hydrogen atom or an alkyl group), divalent aliphatic hydrocarbon groups (for example, alkylene, cycloalkylene, alkenylene (-CH=CH-, etc.) and alkynylene (-C≡C- etc.)), divalent aromatic ring groups (arylylene and heteroarylylene) and groups formed by combining them. In formula (1), the carbon number of the divalent linking group represented by L ¹ is preferably 1 or more, more preferably 1-100, and still more preferably 3-15.

Among them, L ¹ is preferably a group represented by "* ^p -(L ² -Ar) _k -* ^q ". * ^q represents the bonding position on the side directly bonded to the maleimide group, and * ^p represents the bonding position on the opposite side. k represents an integer of 1 or more, preferably 1 to 10, more preferably 1. L ² represents a single bond, -C(R ³ )(R ⁴ )-, -O- or -CO-, preferably -C(R ³ )(R ⁴ )-. R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, preferably an alkyl group (which may be linear or branched, having 1 to 10 carbon atoms). Ar represents an aryl group. The number of ring member atoms of the arylylene group is preferably 6 to 15, more preferably 6. When the above-mentioned aryl group has a substituent, the number of substituents is preferably 1 to 4, more preferably 1 to 2. As a substituent which the above-mentioned arylylene group may have, an alkyl group (which may be linear or branched and has 1 to 10 carbon atoms) is preferable. As the structure that Ar can adopt, for example, a structure that can be formed by the phenyl ring group bonded to R ¹ and R ² shown in formula (1) can also be mentioned. When there are plural L ² and Ar, the plural L ² and the plural Ar may be the same as or different from each other.

When n is 1, on the phenyl ring group bonded to R ¹ and R ² , the maleimide group and the "-(L ¹ ) _m -maleimide group" The two groups represented by the group may be arranged in the ortho position, the meta position, or the para position. Among them, it is preferred that the above two groups are arranged at the meta-position or the para-position.

Among them, regarding the compound represented by formula (1), m represents 1, n represents 1, and the carbon number of the divalent linking group represented by L ¹ is preferably 3-15.

As for the maleimide compound, only one type may be used, or two or more types may be used. The content of the maleimide compound is preferably from 0.1 to 40% by mass, more preferably from 1 to 15% by mass, and still more preferably from 3.5 to 8% by mass, based on the total solid content of the composition. The content of the maleimide compound is preferably from 1 to 200% by mass, more preferably from 5 to 100% by mass, more preferably from 10 to 70% by mass, with respect to the total content of the epoxy compound and the phenolic compound, and 20% by mass. -60 mass % is still more preferable. The content of the maleimide compound relative to the content of the phenolic compound is, for example, preferably 1 to 500% by mass, more preferably 20 to 300% by mass, further preferably 50 to 200% by mass, and 70 to 130% by mass. Quality % is especially good.

〔Hardening Accelerator〕 It is preferable that the composition further contains a curing accelerator. Examples of the hardening accelerator include tri-o-tolylphosphine, triphenylphosphine, boron trifluoride amine complexes, compounds described in paragraph [0052] of JP-A-2012-067225, four Tetraphenylphosphonium tetraphenylborate (TPP-K), tetraphenylphosphonium tetra-p-tolylborate (TPP-MK), tetra-n-butylphosphonium laurate ( Tetra-n-butylphosphonium laurate) (TBP-LA), bis(tetra-n-butylphosphonium) pyromellitic acid ester and bis(naphthalene-2,3-dioxy)phenylsilicate of tetraphenylphosphonium Onium salt-based hardening accelerators such as quaternary phosphonium-based compounds (phosphonium salts) such as adducts. Also, as the hardening accelerator, for example, 2-methylimidazole (product name; 2MZ), 2-undecylimidazole (product name; C11-Z), 2-heptadecylimidazole (product name; C17Z), 1,2-dimethylimidazole (product name; 1.2DMZ), 2-ethyl-4-methylimidazole (product name; 2E4MZ), 2-phenylimidazole (product name; 2PZ), 2- Phenyl-4-methylimidazole (product name; 2P4MZ), 1-Benzyl-2-methylimidazole (product name; 1B2MZ), 1-Benzyl-2-phenylimidazole (product name; 1B2PZ), 1 -Cyanoethyl-2-methylimidazole (product name; 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (product name; C11Z-CN), 1-cyanoethyl-2-benzimidazole Trimer (product name; 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-same trisylamine (product name; 2MZ-A ), 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-sesame (product name; C11Z-A), 2,4-diamino -6-[2'-Ethyl-4'-methylimidazolyl-(1')]-ethyl-sestrimethanone (product name; 2E4MZ-A), 2,4-diamino-6-[ 2'-Methylimidazolyl-(1')]-Ethyl-Mes-3-Isocyanuric Acid Adduct (Product Name; 2MA-OK), 2-Phenyl-4,5-Dihydroxymethyl Imidazole (product name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name; 2P4MHZ-PW), 1-cyanoethyl-2-phenylimidazole (product name; 2PZ-CN), 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-Ethyl-Mestrisulfone (product name; 2MZA-PW) and 2,4-Diamino Amino-6-[2'-methylimidazolyl-(1')]-ethyl-isocyanuric acid adduct (product name; 2MAOK-PW) and other imidazole-based hardening accelerators (homogeneous Manufactured for SHIKOKU CHEMICALS CORPORATION). In addition, examples of the triarylphosphine-based curing accelerator include compounds described in paragraph [0052] of JP-A-2004-043405. Examples of the phosphorus-based hardening accelerator obtained by adding triphenylborane to triarylphosphine include compounds described in paragraph [0024] of JP-A-2014-005382.

Among them, 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 hardening accelerator may be a compound containing a phosphorus atom or a phosphonium salt itself. When using a phosphonium salt as a hardening accelerator, the storage stability of the semi-cured film formed from a composition is excellent.

A hardening accelerator may be used individually by 1 type, and may use 2 or more types. The content of the hardening accelerator is preferably at least 0.002% by mass, more preferably at least 0.02% by mass, and still more preferably at least 0.07% by mass, based on the total solid content of the composition. The upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less with respect to the total solid content of the composition. The content of the hardening accelerator is preferably at least 0.01% by mass, more preferably at least 0.10% by mass, and still more preferably at least 0.55% by mass, based on all the epoxy compounds. The upper limit is preferably at most 40% by mass, more preferably at most 12% by mass, further preferably at most 10% by mass, and particularly preferably at most 5% by mass, based on all epoxy compounds. The content of the compound having a phosphorus atom or the phosphonium salt is preferably from 10 to 100% by mass, more preferably from 50 to 100% by mass, and still more preferably from 80 to 100% by mass, based on the total mass of the hardening accelerator.

〔Ion Scavenger〕 It is preferable that the composition of the present invention further contains an ion-scavenging agent from the viewpoint of excellent insulating properties of the heat-conducting material. The ion scavenger adsorbs ionic impurities in the composition or in the thermally conductive material formed using the composition. As an ion trapping agent, an inorganic type ion trapping agent and an organic type ion trapping agent are mentioned, for example. In addition, all or a part of the above-mentioned specific inorganic substances and other inorganic substances may also function as an ion-scavenging agent.

Examples of inorganic ion capture agents include cation adsorbents that capture cations by ion exchange, anion adsorbents that capture anions by ion exchange, and dual combinations that capture both cations and anions by ion exchange. Inorganic ion adsorbents such as ion traps.

As an inorganic ion-scavenging agent, for example, an inorganic substance (preferably a composite) containing one or more (preferably two or more) selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, and magnesium can be mentioned. Inorganic matter). Examples of inorganic substances (preferably composite inorganic substances) containing one or more (preferably two or more) of the above include oxides (preferably composite oxides), oxidized hydrates (preferably composite oxidized hydrated substances) and hydroxides (preferably composite hydroxides). Also, as the inorganic ion-scavenging agent, for example, composite inorganic substances (composite oxides, composite oxide hydrates) and aluminum of one or more selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, and magnesium can also be mentioned. substances and composite hydroxides, etc.). As a composite oxide, for example, an alumina/magnesia solid solution is mentioned.

The inorganic ion scavenger as a composite is two or more selected from the group consisting of antimony, bismuth, zirconium, magnesium and aluminum, an oxide (composite oxide), an oxide hydrate (composite oxide hydrate) or Hydroxide (composite hydroxide) is preferred. Among them, the inorganic ion-scavenging agent is a three-component composite of magnesium, aluminum, and zirconium (composite oxide, composite oxide hydrate, composite hydroxide, etc.), a two-component composite of bismuth and zirconium (composite oxide, composite oxide hydrate, composite hydroxide, etc.), bismuth and antimony two-component composites (composite oxides, composite oxide hydrates, composite hydroxides, etc.), or composites containing magnesium and aluminum (composite oxides, composite oxides Hydrate and composite hydroxide, etc.) are preferable, bismuth and zirconium two-component composites or magnesium and aluminum two-component composites are more preferable.

When the inorganic ion scavenger contains two or more metal atoms, the content of the inorganic ion scavenger contains two or more (for example, 2 to 4 types) to 1 with respect to all the metal atoms in the inorganic ion scavenger. It is preferably ∼99 mole % of metal atoms, and it is more preferable to contain 2 or more types (for example, 2 to 4 types) so as to be 5 to 95 mole % of metal atoms. The content of the inorganic ion-scavenging agent is preferably 0.01 to 40% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.2 to 10% by mass, based on all the inorganic substances.

Examples of the organic ion-scavenging agent include tristhiol compounds, trisanthamine compounds, benzimidazole compounds, benzotriazole compounds, aminotriazole compounds, and bisphenol-based reducing agents.

Examples of the tristhiol compound include 2-dibutylamino-4,6-dimercapto-siotrithiol. Examples of the benzimidazole compound include benzimidazole. Examples of benzotriazole compounds include 1H-benzotriazole, carboxybenzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzotriazole, 2- (2'-Hydroxy-5'-methylphenyl)benzotriazole and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tertiary octyl phenol]. Examples of the aminotriazole compound include 3-amino-1,2,4-triazole and 3,5-diamino-1,2,4-triazole. Examples of bisphenol-based reducing agents include 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol) and 4,4'-butylenebis-(6-tri-butylphenol) grade butyl-3-methylphenol).

As the ion trapping agent, a commercially available ion trapping agent can be used. Examples of commercially available ion traps include DHF-4A, DHT-4A, DHT-4A-2, DHT-4C, Kyoward500, KW-2000, and KW-2100 (product name, Kyowa Chemical Industry Co. Ltd. .manufactured); IXE-100, IXE-500, IXE-600, IXE-700F, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS-A2 and IXEPLAS-B1 (product name, manufactured by TOAGOSEI CO.,LTD. ); Gisnet DB (product name, manufactured by Sankyo Pharmaceutical Co., Ltd.); VD-3 and VD-5 (product name, manufactured by SHIKOKU CHEMICALS CORPORATION); and Yoshinox BB (product name, manufactured by YOSHITOMI PHARMACEUTICAL INDUSTRIES, LTD.) .

Ion trapping agents 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% by mass relative to the total solid content of the composition, and 0.1 -20 mass % is more preferable, and 0.2-10 mass % is still more preferable. In addition, when the ion scavenger includes an inorganic ion scavenger, a part or all of the ion scavenger may belong to the above-mentioned specific inorganic substance or other inorganic substances at the same time.

〔Solvent〕 The composition may contain a solvent. As a solvent, an organic solvent is preferable. Examples of organic solvents include cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, methylene chloride and tetrahydrofuran. When the composition contains a solvent, the content of the solvent is such that the solid content concentration of the composition is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 50 to 50% by mass. The amount of 80% by mass is further more preferable. The content of the solvent is preferably from 10 to 80% by mass, more preferably from 15 to 70% by mass, and still more preferably from 20 to 50% by mass, based on the total mass of the composition.

〔Manufacturing method of the composition〕 The method for producing the composition is not particularly limited, and a known method can be used, for example, it can be produced by mixing the above-mentioned various components. When mixing, various components may be mixed at once, or may be mixed sequentially. The method of mixing the components is not particularly limited, and known methods can be used. The mixing device used for mixing is preferably a liquid disperser, for example, mixers such as self-rotating mixers, high-speed rotary shear mixers, rubber mills, roller mills, high-pressure jet dispersers, ultrasonic dispersers, etc. machine, bead mill and homogenizer. One type of mixing device may be used alone, or two or more types may be used. The degassing treatment may be performed before and after mixing and/or simultaneously.

〔How to harden the composition〕 The composition of the present invention is preferably a composition for forming a thermally conductive material. A thermally conductive material can be obtained by hardening the composition of the present invention. The curing method of the composition is not particularly limited, and thermal curing reaction is preferred. The heating temperature during the thermosetting reaction is not particularly limited. For example, what is necessary is just to select suitably within the range of 50-250 degreeC. In addition, when the thermosetting reaction is performed, it may be performed through plural times of heat treatment at different temperatures. Hardening treatment is preferably performed on a film-like or sheet-like composition. Specifically, for example, what is necessary is just to apply a composition to form a film, and to perform hardening reaction. When hardening is performed, it is preferable to harden after forming a coating film by coating a composition on a base material. At this time, the curing treatment may be performed after bringing a different base material into contact with the coating film formed on the base material. The cured product (thermally conductive material) obtained after curing may be separated from one or both of the base materials, or may not be separated. In addition, when the hardening treatment is performed, the composition may be applied to each substrate to form coating films, and the hardening treatment may be performed in a state where the obtained coating films are in contact with each other. The cured product (thermally conductive material) obtained after curing may be separated from one or both of the base materials, or may not be separated.

The hardening treatment can be terminated when the composition becomes a semi-hardened state. In addition, after the composition is brought into a semi-cured state, a curing treatment may be further performed to complete the curing. Hardening treatment for bringing the composition into a semi-hardened state (hereinafter, also referred to as "semi-hardening treatment") and hardening treatment for completely hardening it (hereinafter, also referred to as "main curing treatment") may be used. ) are carried out in separate steps.

In the semi-hardening treatment, for example, after coating the composition on the base material to form a coating film, the coating film on the base material can be directly heated in a non-pressurized state to make it a heat-conducting material in a semi-hardened state. (Also known as "semi-cured film" or "semi-hardened sheet"), it is also possible to heat the coating film on the base material while stamping to make it a semi-cured film. In the pressing process, the pressing process may be performed before or after the above-mentioned heating or the like, or may be performed during the heating. When press working is performed during the semi-cured treatment, it may be easy to adjust the film thickness of the obtained semi-cured film and/or to easily reduce the amount of voids in the semi-cured film. In the semi-curing treatment, the semi-curing treatment may be performed in a state where the coating films formed on the respective substrates are laminated, or the semi-curing treatment may be performed without laminating the coating films. The semi-curing treatment may be performed in a state where the coating film formed of the composition is further brought into contact with a material other than the above-mentioned coating film.

The obtained semi-cured film can be directly used as a heat-conducting material, or it can be used as a fully cured heat-conducting material after the main curing treatment is performed on the semi-cured film. In the main hardening treatment, the semi-cured film may be directly heated without pressurization, or may be heated after pressing or while pressing. At this time, in the main curing treatment, the main curing treatment may be performed in a state where the semi-cured films are laminated, or the main curing treatment may be performed without laminating the semi-cured films. In addition, the main curing treatment can be performed in a state where the semi-cured film is placed in contact with the device or the like to be used. It is also preferred to bond the device to the thermally conductive material of the present invention by a main hardening process.

There is no limitation to the press used for the press working during the hardening treatment in the semi-hardening treatment and/or the main hardening treatment, for example, a flat press machine or a roll press machine may be used. In the case of using a roll press machine, for example, a substrate with a coating film obtained by forming a coating film on a substrate is sandwiched between a pair of rollers facing each other, while rotating the pair of rollers and making It is preferable to apply pressure along the film thickness direction of the above-mentioned substrate with a coating film while passing the substrate with a coating film. Regarding the above-mentioned base material with a coating film, the base material may be present on only one surface of the coating film, or may be present on both surfaces of the coating film. The above-mentioned substrate with a coated film may pass through the roller press only once, or may pass through multiple times. When the hardening treatment is performed in the semi-hardening treatment and/or the main hardening treatment, only one of the treatment by a plate press and the treatment by a roll press may be performed, or both may be performed.

Regarding the production of thermally conductive materials including hardening reactions, see "High Thermally Conductive Composite Materials" (published by CMC, written by Yutaka Takezawa).

The shape of the thermally conductive material can be formed into various shapes depending on the usage. As a typical shape of the molded thermally conductive material, for example, a sheet shape is mentioned. That is, it is also preferable that the thermally conductive material obtained by using the composition of the present invention is a thermally conductive sheet. Furthermore, it is preferable that the thermal conductivity of the thermally conductive material obtained by using the composition of the present invention is isotropic rather than anisotropic.

Thermally conductive materials are preferably insulating (electrically insulating). In other words, it is preferable that the composition of the present invention is a thermally conductive insulating composition. The volume resistivity of the thermally conductive material at 23°C and a relative humidity of 65% is preferably 10 ¹⁰ Ω·cm or higher, more preferably 10 ¹² Ω·cm or higher, and still more preferably 10 ¹⁴ Ω·cm or higher. The upper limit is preferably 10 ¹⁸ Ω·cm or less.

〔Applications of thermally conductive materials〕 The thermally conductive material obtained by using the composition of the present invention can be used as a heat dissipation material such as a heat sink, and can be used for heat dissipation of various devices. More specifically, a device with a thermally conductive layer is fabricated 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, so that the heat from the device can be effectively dissipated by the thermally conductive layer. The above-mentioned heat conduction layer may be a heat conduction layer including a heat conduction multilayer sheet described later. Since the thermally conductive material obtained by using the composition of the present invention has sufficient thermal conductivity and high heat resistance, it is suitable for heat dissipation of power semiconductor devices used in electronic equipment such as personal computers, general household appliances, and automobiles. In addition, since the thermally conductive material obtained by using the composition of the present invention has sufficient thermal conductivity even in a semi-hardened state, it can also be used as a gap between components placed in various devices, etc. Parts of the heat dissipation material. Moreover, since adhesiveness is also excellent, it can also be used as an adhesive agent which has thermal conductivity.

The thermally conductive material obtained by using the composition of the present invention can be used in combination with members other than members formed from the composition. For example, a thermally conductive material (thermally conductive sheet, etc.) may be combined with a support (material to be adhered) other than the layer formed of this composition. Examples of the support (material to be adhered) include plastic materials, metal materials, and glass. Examples of plastic materials include polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, and silicones. (silicone). Examples of metal materials include copper and aluminum. It is also preferable that the support (material to be adhered) is in the form of a sheet. The film thickness of the sheet-shaped thermally conductive material (thermally conductive sheet) is preferably 100 to 300 μm, more preferably 150 to 250 μm.

Also, for the thermally conductive material (preferably a thermally conductive sheet), an adhesive layer and/or an adhesive layer can be combined. By bonding the thermally conductive material to an object that needs to transfer heat, such as a device, through the above-mentioned adhesive layer and/or adhesive layer, stronger bonding between the thermally conductive material and the object can be achieved. The thermally conductive material formed from the composition of the present invention has good adhesion to the adhesive layer and the adhesive layer, and can also suppress peeling at the interface between the thermally conductive material and the adhesive layer or the adhesive layer. For example, as a thermally conductive multilayer sheet, a thermally conductive multilayer sheet having a thermally conductive sheet and an adhesive layer or an adhesive layer provided on one or both sides of the thermally conductive sheet can be produced. In addition, one or both of the adhesive layer and the adhesive layer may be respectively provided on one side or both sides of the above-mentioned heat conduction sheet, or both may be provided. An adhesive layer may be provided on one surface of the thermally conductive sheet, and an adhesive layer may be provided on the other surface. In addition, an adhesive layer and/or an adhesive layer may be partially provided on one or both surfaces of the above-mentioned thermally conductive sheet, or may be provided on the entire surface. In addition, 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 heat conductive multilayer sheet may be cured, may be in a semi-cured state, or may be in an uncured state. [Example]

Hereinafter, the present invention will be described in further detail based on examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

[Preparation and Evaluation of Composition] [various ingredients] Various components used in Examples and Comparative Examples are shown below.

＜Phenolic compounds＞

[chemical formula 31]

＜Epoxy compound＞ The weight average molecular weight of B-8 was 3000, and the average value of the n value of B-9 was 10.

[chemical formula 32]

＜Hardening Accelerator＞ ・C-1: Tri-o-tolylphosphine ・C-2: Triphenylphosphine ・C-3: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) ・C-4: TPP-MK (tetraphenylphosphonium tetra-p-tolyl borate)

＜Specified inorganic substances or surface-modified specified inorganic substances＞ Specific inorganic substances or surface-modifying specific inorganic substances used in each of Examples and Comparative Examples are shown below. Also, in any specific surface-modified inorganic substance, the content of the surface-modifying agent is more than 0% by mass and less than 1% by mass relative to the total mass of the specified surface-modified inorganic substance.

＜Condensed Boron Nitride＞ ・HP-40: Condensed 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 the production method A shown below ・BN-B: Surface-modified agglomerated boron nitride produced by the production method B shown below ・BN-C: Surface-modified condensed boron nitride produced by the production method C shown below ・BN-D: Surface-modified agglomerated boron nitride produced by the production method D shown below ・BN-E: Surface-modified agglomerated boron nitride produced by the production method E shown below

(Manufacturing method A) Condensed boron nitride (HP-40 MF100) (15 g) was subjected to vacuum plasma treatment (gas types: O ₂ , Pressure: 30Pa, output: 500W). When the vacuum plasma treatment was performed for 5 minutes, the condensed boron nitride to be treated was stirred, and the vacuum plasma treatment was performed until the total treatment time reached 30 minutes, and modified boron nitride particles A were obtained. The obtained modified boron nitride particles A were stirred in acetonitrile (30 ml), and a hydrolysis adjustment solution (0.42 g). The above-mentioned acetonitrile was stirred at room temperature for 3 hours to carry out adsorption treatment. After filtering and taking out the above-mentioned modified boron nitride particles A in acetonitrile, the filtered and taken-out modified boron nitride particles A were washed with acetonitrile (30 ml), and dried in an oven at 40° C., thereby obtaining BN- a. In addition, a hydrolysis-adjusted 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. liquid. In the following examples or comparative examples, unless otherwise specified, the blending of the hydrolysis adjustment solution of the silane coupling agent is also the same. Also, "X12-984S" is a polymer-type silane coupling agent having an epoxy group and an ethoxysilyl group.

(Manufacturing method B) Agglomerated boron nitride (HP-40 MF-100, 50 g) was added to an aqueous NaOH solution (NaOH: 40 g/water: 400 ml) and stirred. After further adding sodium persulfate water (sodium persulfate: 9.6 g/water: 100 ml) to the above NaOH aqueous solution, the above NaOH aqueous solution was heated to 50° C. and further stirred for 3 hours. Stirring was performed at a rotation speed of 150 rpm using a three-in-one motor (manufactured by Shinto Scientific Co., Ltd.). After cooling the above-mentioned NaOH aqueous solution to room temperature, filter and take out the agglomerated boron nitride particles B in the above-mentioned NaOH aqueous solution, wash the filtered and taken-out agglomerated boron nitride particles B with water (500ml) and acetonitrile (250ml), thereby Modified boron nitride particles B were obtained. The obtained modified boron nitride particles B were stirred in acetonitrile (100 ml), and a hydrolysis adjustment solution (1.25 g). The above-mentioned acetonitrile was stirred at room temperature for 3 hours, and adsorption treatment was performed. After filtering and taking out the above-mentioned modified boron nitride particles B in acetonitrile, the filtered and taken-out modified boron nitride particles B were washed with acetonitrile (100 ml), and dried in an oven at 40° C., thereby obtaining BN- b.

(Manufacturing method C) A mixed solution was obtained by adding and stirring boron nitride (HP-40 MF-100, 50 g) to water (400 ml). After sodium hypochlorite water (sodium hypochlorite pentahydrate: 48 g/water: 100 ml) was further added to the above mixed liquid, the temperature of the above mixed liquid was raised to 50° C. and further stirred for 3 hours. Stirring was performed at 150 rpm using a three-in-one motor (manufactured by Shinto Scientific Co., Ltd.) during stirring. After the above-mentioned mixed solution is cooled to room temperature, filter and take out the agglomerated boron nitride particles in the above-mentioned mixed solution, wash the filtered and taken-out agglomerated boron nitride particles with water (500ml) and acetonitrile (250ml), thereby obtaining Modified boron nitride particles C. The obtained 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 above-mentioned acetonitrile was stirred at room temperature for 3 hours, and adsorption treatment was performed. After filtering and taking out the above-mentioned modified boron nitride particles C in acetonitrile, the filtered and taken-out modified boron nitride particles C were washed with acetonitrile (100 ml), and dried in an oven at 40° C., thereby obtaining BN- c.

(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. After reslurrying and washing with water (500ml) and filtering the obtained modified boron nitride particles D, they were stirred in acetonitrile (100ml) and hydrolyzed by adding a silane coupling agent (KBM-403) to the acetonitrile Adjusting solution (1.25g). The above-mentioned acetonitrile was stirred at room temperature for 3 hours, and adsorption treatment was performed. After filtering and taking out the above-mentioned modified boron nitride particles D in acetonitrile, the filtered and taken-out modified boron nitride particles D were washed with acetonitrile (100 ml), and dried in an oven at 40° C., thereby obtaining BN- d.

(Manufacturing method E) Agglomerated boron nitride (HP-40 MF-100, 50 g) was heated at 900° C. for 4 hours to obtain modified boron nitride particles E. After reslurrying and washing with water (500ml) and filtering the obtained modified boron nitride particles E, they were stirred in acetonitrile (100ml) and hydrolyzed by adding a silane coupling agent (KBM-403) to the acetonitrile Adjusting solution (1.25g). The above-mentioned acetonitrile was stirred at room temperature for 3 hours, and adsorption treatment was performed. After filtering and taking out the above-mentioned modified boron nitride particles E in acetonitrile, the filtered and taken-out modified boron nitride particles E were washed with acetonitrile (100 ml), and dried in an oven at 40° C., thereby obtaining BN- e.

＜Inorganic X＞ ・AA-03F: Aluminum oxide (average particle size: 0.25μm, manufactured by Sumitomo Chemical Co., Ltd.) ・Surface modification AA-03F: Surface modification alumina (average particle size: 0.25 μm, manufactured by Sumitomo Chemical Co., Ltd.) ・QSG-100: Surface-modified silica (average particle size: 0.11 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) ・QSG-10: Surface-modified silica (average particle size: 0.015μm, manufactured by Shin-Etsu Chemical Co., Ltd.)

＜Inorganic substance Y＞ ・Surface modification AA-3: Surface modification alumina (average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd., equivalent to other surface modification inorganic substances) ・AA-04: Aluminum oxide (average particle size: 0.40 μm, manufactured by Sumitomo Chemical Co., Ltd.)

＜Maleimide compound＞ ・F-1: Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane) (FUJIFILM Corporation manufacture)

＜Acid anhydride＞ ・H-1: Styrene maleic anhydride copolymer (XIRAN EF-40, manufactured by Polyscope Polymers B.V.)

<Ion Scavenger> ・G-1: KW-2000, alumina/magnesia solid solution (Mg _0.7 Al _0.3 O _1.15 ), manufactured by Kyowa Chemical Industry Co. Ltd. ・G-2: IXE-6107, Zr, Bi-based (manufactured by TOAGOSEI CO.,LTD.)

<Solvent> As a solvent, cyclopentanone was used.

〔Preparation of composition〕 A mixture in which epoxy compounds and phenol compounds in combinations shown in Table 1 below were blended in an equivalent amount (an amount in which the number of epoxy groups of the epoxy compound is equal to the number of hydroxyl groups of the phenol compound) was prepared. After mixing the above-mentioned mixture, solvent, ion scavenger if necessary, acid anhydride if necessary, maleimide compound and hardening accelerator if necessary, specific inorganic substances and surface modification are added Specific inorganic substances or inorganic substance Y added as needed. The obtained mixture was processed for 5 minutes with an autorotation-revolving mixer (manufactured by THINKY CORPORATION., Awatori Netaro ARE-310) to obtain compositions (curable compositions) of each Example or each Comparative Example.

The addition amount of the solvent in each Example and each comparative example was made into the amount which made the solid content concentration of the composition of each Example and each comparative example 50-80 mass %. In addition, the solid content concentration of the composition was adjusted for each composition within the above-mentioned range so that the viscosity of the composition was substantially the same. Adjust the addition amount so that the total content of the epoxy compound and the phenolic compound becomes the amount shown in the "total amount (mass %)" column in Table 1 with respect to the total solid content of the composition, and the epoxy compound and the phenolic compound The compounds are equivalent (the number of epoxy groups of the epoxy compound and the number of hydroxyl groups of the phenol compound are equal).

[Evaluation] 〔Production of semi-hardened sheet (semi-hardened film)〕 Using an applicator attached to a micrometer, the prepared composition was uniformly coated on the release surface of a release-treated PET film (PET756501 manufactured by LINTEC Corporation, film thickness 75 μm), and dried at 120° C. for 4 The semi-hardened sheet (semi-hardened film) was produced in minutes.

〔Production of thermally conductive sheet (semi-cured film)〕 The obtained semi-hardened sheet was covered with a release-treated PET film, and hot-pressed in air (at a hot plate temperature of 180° C. and a pressure of 5 MPa for 5 minutes). Then, it heat-processed at 180 degreeC for 90 minutes under normal pressure, and obtained the resin sheet. The PET films present on both sides of the resin sheet were peeled off to obtain a heat conduction sheet (heat conduction material) with an average film thickness of 120 μm.

〔Evaluation of thermal conductivity〕 Thermal conductivity was evaluated using the thermally conductive sheet obtained in the above [Preparation of thermally conductive sheet (semi-cured film)]. (1) Using "LFA467" manufactured by NETZSCH, the thermal diffusivity in the thickness direction of the thermally conductive sheet was measured by the laser flash method. (2) Using the balance "XS204" manufactured by METTLER TOLEDO, the specific gravity of the thermal conductive sheet was measured using the Archimedes method (using the "solid specific gravity measurement kit"). (3) Using "DSC320/6200" manufactured by Seiko Instruments Inc., the specific heat of the thermally conductive sheet at 25°C was determined under the temperature rise condition of 10°C/min. (4) Calculate the thermal conductivity of the heat conduction sheet by multiplying the obtained thermal diffusivity by the specific gravity and specific heat.

The thermal conductivity of the thermally conductive sheet was classified with reference to the following criteria to evaluate the thermal conductivity of the thermally conductive sheet (thermally conductive material) obtained using the composition of each Example or each comparative example. A ⁺ : above 17W/mK A: above 15W/mK and less than 17W/mK B: above 13W/mK and below 15W/mK C: above 10W/mK and below 13W/mK D: below 10W/mK

[Evaluation of heat resistance (Tg)] The Tg of the thermally conductive sheet obtained in the above [Production of the thermally conductive sheet (semi-cured film)] was measured. For the measurement, a dynamic viscoelasticity measuring device "Rheogel-E4000" manufactured by Universal Building Materials Co., Ltd. was used, and the tan δ peak at a frequency of 1 Hz was defined as Tg. The temperature increase rate was 5°C/min, and the measurement was carried out in the range of 25 to 300°C.

The Tg of the thermally conductive sheet was classified with reference to the following criteria to evaluate the heat resistance of the thermally conductive sheet (thermally conductive material) obtained using the composition of each Example or each Comparative Example. A: Above 170°C B: Above 160°C and below 170°C C: less than 160°C

〔Evaluation of insulation〕 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 dielectric breakdown of the sample was measured. The time until the insulation of the samples broke the soil was classified with reference to the following criteria to evaluate the insulation properties of the thermally conductive sheets (thermally conductive materials) obtained using the compositions of each Example or each Comparative Example. A: More than 500 hours B: More than 100 hours and less than 500 hours C: less than 100 hours

〔Evaluation of solder heat resistance〕 The semi-hardened sheet obtained in the above [production of semi-hardened sheet (semi-hardened film)] is sandwiched between a copper substrate with a thickness of 2mm and a copper foil with a thickness of 0.15mm, and hot-pressed under air (at the temperature of the hot plate 180°C, 5 minutes at a pressure of 5MPa), thus obtaining a laminate with a structure of "copper substrate-heat conduction sheet-copper foil". The 0.15 mm copper foil in the obtained laminate was etched to a circular shape with a diameter of 2 cm, and the above laminate was used as "copper substrate-heat conduction sheet-circular copper foil with a diameter of 2 cm" The structure of the sample used in the solder heat resistance test. The above sample was heated at 300° C. for 5 minutes and then cooled to room temperature (25° C.) for three times. Then, in the obtained sample, a circular copper foil having a diameter of 2 cm was peeled off. The fractured state of the peeled sample was visually observed to confirm whether interfacial peeling had occurred on a part or the entire surface between the "copper substrate and the thermally conductive sheet", and the solder heat resistance of the thermally conductive sheet was evaluated referring to the following classification. A: Interfacial peeling was not confirmed on a part or the entire surface between the "copper substrate and the heat transfer sheet". B: Interfacial delamination was confirmed in a part between "copper substrate-heat conduction sheet". C: Interfacial peeling was confirmed on the entire surface between the "copper substrate and the thermally conductive sheet".

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

[Table 1] hardening composition Evaluation Phenolic Compounds and Epoxy Compounds Hardening Accelerator (C) Condensed boron nitride (D) Inorganic Y (I) Inorganic X (E) (D) /(E) (D) /(E+I) additive Phenolic compounds (A) Epoxy compound (B) Total amount (mass%) Maleimide compound (F) Anhydride (H) Ion Scavenger (G) thermal conductivity heat resistance insulation Solder heat resistance type type type Content (mass%) type Average particle size (μm) Content (mass%) type Average particle size (μm) Content (mass%) type Average particle size (μm) Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) Example 1 A-2 B-3 13.9 C-1 0.1 HP-40 40 60 - - - AA-03F 0.25 20 3.0 - F-1 5 - - G-1 1 C A A A Example 2 A-2 B-3 13.9 C-1 0.1 HP-40 40 70 - - - AA-03F 0.25 10 7.0 - F-1 5 - - G-1 1 B A A A Example 3 A-2 B-3 13.9 C-1 0.1 HP-40 40 75 - - - AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 4 A-2 B-3 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 5 A-2 B-3 18.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - - - - - G-1 1 A B A A Example 6 A-2 B-3 19.9 C-1 0.1 HP-40 40 70 - - - Surface modification AA-03F 0.25 5 14.0 - F-1 5 - - - - A A B A Example 7 A-1 B-3 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 8 A-2 B-1 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 9 A-2 B-2 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 10 A-2 B-4 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 11 A-2 B-5 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 12 A-2 B-6 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 13 A-2 B-7 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 14 A-2 B-8 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 15 A-2 B-9 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 16 A-2 B-10 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 17 A-2 B-11 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 B B B B Example 18 A-2 B-3 13.9 C-1 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-2 1 A A A A Example 19 A-2 B-3 13.9 C-2 0.1 HP-40 40 75 - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 20 A-2 B-3 13.9 C-3 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 21 A-2 B-3 13.9 C-4 0.1 HP-40 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A A A A Example 22 A-2 B-3 13.9 C-1 0.1 BN-A 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 23 A-2 B-3 13.9 C-1 0.1 BN-B 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 24 A-2 B-3 13.9 C-1 0.1 BN-C 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A

[Table 2] hardening composition Evaluation Phenolic Compounds and Epoxy Compounds Hardening Accelerator (C) Condensed boron nitride (D) Inorganic Y (I) Inorganic X (E) (D) /(E) (D) /(E+I) additive Phenolic compounds (A) Epoxy compound (B) Total amount (mass%) Maleimide compound (F) Anhydride (H) Ion Scavenger (G) thermal conductivity heat resistance insulation Solder heat resistance type type type Content (mass%) type Average particle size (μm) Content (mass%) type Average particle size (μm) Content (mass%) type Average particle size (μm) Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) Example 25 A-2 B-3 13.9 C-1 0.1 BN-D 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 26 A-2 B-3 13.9 C-1 0.1 BN-E 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 27 A-2 B-3 13.9 C-1 0.1 BN-A 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - - - H-1 5 G-1 1 A ⁺ B A A Example 28 A-2 B-3 13.9 C-1 0.1 BN-B 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - - - H-1 5 G-1 1 A ⁺ B A A Example 29 A-2 B-3 13.9 C-1 0.1 BN-C 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - - - H-1 5 G-1 1 A ⁺ B A A Example 30 A-2 B-3 13.9 C-1 0.1 BN-D 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - - - H-1 5 G-1 1 A ⁺ B A A Example 31 A-2 B-3 13.9 C-1 0.1 BN-E 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - - - H-1 5 G-1 1 A ⁺ B A A Example 32 A-2 B-3 8.9 C-1 0.1 BN-A 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 H-1 5 G-1 1 A ⁺ A A A Example 33 A-2 B-3 8.9 C-1 0.1 BN-B 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 H-1 5 G-1 1 A ⁺ A A A Example 34 A-2 B-3 8.9 C-1 0.1 BN-C 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 H-1 5 G-1 1 A ⁺ A A A Example 35 A-2 B-3 8.9 C-1 0.1 BN-D 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 H-1 5 G-1 1 A ⁺ A A A Example 36 A-2 B-3 8.9 C-1 0.1 BN-E 40 75 - - - Surface modification AA-03F 0.25 5 15.0 - F-1 5 H-1 5 G-1 1 A ⁺ A A A Example 37 A-2 B-3 13.9 C-1 0.1 BN-A 40 68 - - - Surface modification AA-03F 0.25 12 5.7 - - - H-1 5 G-1 1 A ⁺ B A A Example 38 A-2 B-3 13.9 C-1 0.1 BN-A 40 68 Surface modification AA-3 3 4 Surface modification AA-03F 0.25 8 8.5 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 39 A-2 B-3 13.9 C-1 0.1 BN-A 40 68 Surface modification AA-3 3 6 Surface modification AA-03F 0.25 6 11.3 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 40 A-2 B-3 13.9 C-1 0.1 BN-A 40 68 Surface modification AA-3 3 8 Surface modification AA-03F 0.25 4 17.0 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 41 A-2 B-3 13.9 C-1 0.1 BN-A 40 68 Surface modification AA-3 3 9 Surface modification AA-03F 0.25 3 22.7 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 42 A-2 B-3 13.9 C-1 0.1 BN-B 40 68 - - Surface modification AA-03F 0.25 12 5.7 - - - H-1 5 G-1 1 A ⁺ B A A Example 43 A-2 B-3 13.9 C-1 0.1 BN-B 40 68 Surface modification AA-3 3 4 Surface modification AA-03F 0.25 8 8.5 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 44 A-2 B-3 13.9 C-1 0.1 BN-B 40 68 Surface modification AA-3 3 6 Surface modification AA-03F 0.25 6 11.3 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 45 A-2 B-3 13.9 C-1 0.1 BN-B 40 68 Surface modification AA-3 3 8 Surface modification AA-03F 0.25 4 17.0 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 46 A-2 B-3 13.9 C-1 0.1 BN-B 40 68 Surface modification AA-3 3 9 Surface modification AA-03F 0.25 3 22.7 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 47 A-2 B-3 13.9 C-1 0.1 BN-C 40 68 - - - Surface modification AA-03F 0.25 12 5.7 - - - H-1 5 G-1 1 A ⁺ B A A Example 48 A-2 B-3 13.9 C-1 0.1 BN-C 40 68 Surface modification AA-3 3 4 Surface modification AA-03F 0.25 8 8.5 5.7 - - H-1 5 G-1 1 A ⁺ B A A

[table 3] hardening composition Evaluation Phenolic Compounds and Epoxy Compounds Hardening Accelerator (C) Condensed boron nitride (D) Inorganic Y (I) Inorganic X (E) (D) /(E) (D) /(E+I) additive Phenolic compounds (A) Epoxy compound (B) Total amount (mass%) Maleimide compound (F) Anhydride (H) Ion Scavenger (G) thermal conductivity heat resistance insulation Solder heat resistance type type type Content (mass%) type Average particle size (μm) Content (mass%) type Average particle size (μm) Content (mass%) type Average particle size (μm) Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) Example 49 A-2 B-3 13.9 C-1 0.1 BN-C 40 68 Surface modification AA-3 3 6 Surface modification AA-03F 0.25 6 11.3 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 50 A-2 B-3 13.9 C-1 0.1 BN-C 40 68 Surface modification AA-3 3 8 Surface modification AA-03F 0.25 4 17.0 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 51 A-2 B-3 13.9 C-1 0.1 BN-C 40 68 Surface modification AA-3 3 9 Surface modification AA-03F 0.25 3 22.7 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 52 A-2 B-3 13.9 C-1 0.1 BN-D 40 68 - - - Surface modification AA-03F 0.25 12 5.7 - - - H-1 5 G-1 1 A ⁺ B A A Example 53 A-2 B-3 13.9 C-1 0.1 BN-D 40 68 Surface modification AA-3 3 4 Surface modification AA-03F 0.25 8 8.5 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 54 A-2 B-3 13.9 C-1 0.1 BN-D 40 68 Surface modification AA-3 3 6 Surface modification AA-03F 0.25 6 11.3 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 55 A-2 B-3 13.9 C-1 0.1 BN-D 40 68 Surface modification AA-3 3 8 Surface modification AA-03F 0.25 4 17.0 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 56 A-2 B-3 13.9 C-1 0.1 BN-D 40 68 Surface modification AA-3 3 9 Surface modification AA-03F 0.25 3 22.7 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 57 A-2 B-3 13.9 C-1 0.1 BN-E 40 68 - - - Surface modification AA-03F 0.25 12 5.7 - - - H-1 5 G-1 1 A ⁺ B A A Example 58 A-2 B-3 13.9 C-1 0.1 BN-E 40 68 Surface modification AA-3 3 4 Surface modification AA-03F 0.25 8 8.5 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 59 A-2 B-3 13.9 C-1 0.1 BN-E 40 68 Surface modification AA-3 3 6 Surface modification AA-03F 0.25 6 11.3 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 60 A-2 B-3 13.9 C-1 0.1 BN-E 40 68 Surface modification AA-3 3 8 Surface modification AA-03F 0.25 4 17.0 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 61 A-2 B-3 13.9 C-1 0.1 BN-E 40 68 Surface modification AA-3 3 9 Surface modification AA-03F 0.25 3 22.7 5.7 - - H-1 5 G-1 1 A ⁺ B A A Example 62 A-2 B-3 13.9 C-1 0.1 BN-A 40 75 - - - QSG-100 0.11 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 63 A-2 B-3 13.9 C-1 0.1 BN-B 40 75 - - - QSG-100 0.11 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 64 A-2 B-3 13.9 C-1 0.1 BN-C 40 75 - - - QSG-100 0.11 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 65 A-2 B-3 13.9 C-1 0.1 BN-D 40 75 - - - QSG-100 0.11 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 66 A-2 B-3 13.9 C-1 0.1 BN-E 40 75 - - - QSG-100 0.11 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 67 A-2 B-3 13.9 C-1 0.1 BN-A 40 75 - - - QSG-100 0.015 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 68 A-2 B-3 13.9 C-1 0.1 BN-B 40 75 - - - QSG-10 0.015 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 69 A-2 B-3 13.9 C-1 0.1 BN-C 40 75 - - - QSG-10 0.015 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 70 A-2 B-3 13.9 C-1 0.1 BN-D 40 75 - - - QSG-10 0.015 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Example 71 A-2 B-3 13.9 C-1 0.1 BN-E 40 75 - - - QSG-10 0.015 5 15.0 - F-1 5 - - G-1 1 A ⁺ A A A Comparative example 1 A-1 B-9 19.9 C-4 0.1 HP-40 40 80 - - - - - - - - - - - - - - D. C C C Comparative example 2 A-1 B-9 19.9 C-1 0.1 HP-40 40 75 AA-04 0.40 5 - - - - - - - - - - - D. C C C

From the results shown in the table, it was confirmed that the effect of the present invention can be achieved by using the composition of the present invention. It was confirmed that the effect of the present invention is more excellent when 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 (comparison of Examples 1 to 3 and 37 to 61). It was confirmed that the effect of the present invention is more effective when the composition further contains a surface modifier and the aggregated boron nitride constitutes the surface-modified aggregated boron nitride together with the surface modifier adsorbed on the surface of the aggregated boron nitride. Excellent (comparison of Examples 22 to 26 and Example 4). It was confirmed that the effect of the present invention is more excellent when the phenolic compound contains a phenolic compound having a three-skeleton skeleton and the epoxy compound contains an epoxy compound having a three-skeleton skeleton is satisfied (Example 4 and Example 17 comparison). It was confirmed that when the composition further contained an ion-scavenging agent, the insulation was more excellent (comparison of Examples 4 and 6). It was confirmed that when the composition further contained a maleimide compound, Tg (heat resistance) was more excellent (comparison of Examples 4 and 5).

none.

Claims (12)

A curable composition containing phenolic compound, epoxy compound, condensed boron nitride and inorganic substance X, The aforementioned inorganic substance X is at least one selected from the group consisting of alumina and silicon dioxide, The average particle size of the agglomerated boron nitride is 20 μm or more, The average particle diameter of the above-mentioned inorganic substance X is 0.30 μm or less. The curable composition as described in Claim 1, wherein The average particle diameter of the above-mentioned inorganic substance X is 0.25 μm or less. The curable composition as described in Claim 1 or Claim 2, wherein The mass ratio of the content of the aforementioned aggregated boron nitride to the content of the aforementioned inorganic substance X is 5.0-25.0. The curable composition according to claim 1 or claim 2, which further contains a surface modifier, The condensed boron nitride and the surface modifier adsorbed on the surface of the condensed boron nitride constitute surface-modified condensed boron nitride. The curable composition according to claim 1 or claim 2, which satisfies at least one of the requirements that the phenol compound includes a phenol compound having a three-skeleton skeleton and the epoxy compound includes an epoxy compound having a three-skeleton skeleton. The curable composition according to Claim 1 or Claim 2, further comprising a curing accelerator. The curable composition as described in Claim 6, wherein The aforementioned hardening accelerator contains a compound having a phosphorus atom. The curable composition according to Claim 1 or Claim 2, further comprising an ion-scavenging agent. The curable composition according to Claim 1 or Claim 2, further comprising a maleimide compound. A thermally conductive material obtained by curing the curable composition described in any one of claim 1 to claim 9. A thermally conductive sheet made of the thermally conductive material described in Claim 10. A device with a heat-conducting layer, comprising: a device; and a heat-conducting layer comprising the heat-conducting material described in Claim 10 disposed on the aforementioned device.