WO2022080078A1

WO2022080078A1 - Curable composition, thermally conductive material, thermally conductive sheet, and device with thermally conductive layer

Info

Publication number: WO2022080078A1
Application number: PCT/JP2021/033948
Authority: WO
Inventors: 誠一人見; 大介林; 慶太高橋; 輝樹新居; 信小澤; 明希中道
Original assignee: 富士フイルム株式会社
Priority date: 2020-10-16
Filing date: 2021-09-15
Publication date: 2022-04-21
Also published as: JPWO2022080078A1; TW202229505A

Abstract

The present invention provides a curable composition giving thermally conductive materials excellent in terms of thermal conductivity and heat resistance, a thermally conductive material, a thermally conductive sheet, and a device with a thermally conductive layer. This curable composition comprises a phenol compound, a maleimide compound having one or more maleimide groups and/or a cyanate compound having one or more cyanate groups, and an inorganic substance, wherein the inorganic substance comprises an inorganic nitride.

Description

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

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

In recent years, power semiconductor devices used in various electric devices such as personal computers, general household appliances, and automobiles have been rapidly miniaturized. With the miniaturization, it is difficult to control the heat generated from the power semiconductor device whose density has been increased.
In order to deal with such a problem, a heat conductive material that promotes heat dissipation from a power semiconductor device is used.
For example, Patent Document 1 describes an epoxy resin containing a polyfunctional epoxy resin, a curing agent containing a novolak resin having a predetermined structural unit, and a nitride as a resin composition capable of achieving high thermal conductivity after curing. A resin composition containing an inorganic filler containing particles is mentioned (claim 1).

Japanese Unexamined Patent Publication No. 2016-104862

By the way, the heat conductive material is required to have not only excellent heat conductivity but also excellent heat resistance in which performance is less likely to deteriorate even when continuously used at a high temperature.
The deterioration of the performance of the heat conductive material at high temperature is due to the insufficient Tg (glass transition point) of the heat conductive material. That is, if the Tg of the heat conductive material is insufficient, the adhesion between the heat conductive material and the object to which the heat transfer material should transfer becomes weak at high temperature, and the heat conductive material is removed from the object. The efficiency of heat transfer deteriorates. If the Tg of the heat conductive material is sufficiently high, the heat conductive material can continue to exhibit excellent heat conductivity, and the heat resistance becomes good. In the present specification, a high Tg of the heat conductive material is also referred to as excellent heat resistance of the heat conductive material.

In view of the above circumstances, it is an object of the present invention to provide a curable composition that provides a heat conductive material having excellent heat conductivity and heat resistance.
Another object of the present invention is to provide a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer relating to the curable composition.

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

[1]
Phenolic compounds and
One or both of a maleimide compound having one or more maleimide groups and a cyanate compound having one or more cyanate groups.
Inorganic, including
A curable composition in which the above-mentioned inorganic substance contains an inorganic nitride.
[2]
Contains the above maleimide compounds
The curable composition according to [1], wherein the maleimide compound is a compound represented by the general formula (1).

In the general formula (1), m represents 0 or 1.
n represents 0 or 1.
R ¹ and R ² independently represent a hydrogen atom or a substituent.
L ¹ represents a divalent linking group.
[3]
The curability according to [2], wherein in the general formula (1), m represents 1, n represents ¹ , and the divalent linking group represented by L1 has 3 to 15 carbon atoms. Composition.
[4]
Contains the above maleimide compounds
The curable composition according to any one of [1] to [3], wherein the maleimide compound has two maleimide groups.
[5]
The curable composition according to any one of [1] to [4], wherein the inorganic substance contains boron nitride.
[6]
The curable composition according to [5], wherein the boron nitride contains aggregated boron nitride having an average particle size of 20 μm or more.
[7]
In addition, it contains a surface modifier and
The curable composition according to [5] or [6], wherein the boron nitride constitutes a surface-modified boron nitride together with the surface modifier adsorbed on the surface of the boron nitride.
[8]
The curable composition according to any one of [1] to [7], further comprising an epoxy compound.
[9]
Contains the above maleimide compound and
The curable composition according to [8], wherein the epoxy compound contains an epoxy compound having a viscosity at 25 ° C. of less than 1000 mPa · s.
[10]
Contains the above maleimide compound and
In the curable composition, the ratio of the number of hydroxyl groups contained in the phenol compound to the total number of epoxy groups contained in the epoxy compound is 1.2 / 1.0 to 2.0 / 1.0. The curable composition according to [8] or [9].
[11]
The present invention according to any one of [8] to [10], wherein the phenol compound satisfies at least one of the requirements that the phenol compound has a triazine skeleton and the epoxy compound contains an epoxy compound having a triazine skeleton. Curable composition.
[12]
The curable composition according to any one of [1] to [11], further comprising a curing accelerator.
[13]
The curable composition according to [12], wherein the curing accelerator contains a compound containing a phosphorus atom.
[14]
The curable composition according to [12] or [13], wherein the curing accelerator contains a phosphonium salt.
[15]
The curable composition according to any one of [12] to [14], wherein the curing accelerator has a molecular weight of 430 or more.
[16]
The curable composition according to [12] or [13], wherein the curing accelerator contains a compound represented by the general formula (P3).

In the general formula (P3), R ^p31 to R ^p34 each independently represent a phenyl group which may have a substituent.
[17]
The curable composition according to any one of [1] to [16], further comprising an ion scavenger.
[18]
A heat conductive material obtained by curing the curable composition according to any one of [1] to [17].
[19]
A heat conductive sheet made of the heat conductive material according to [18].
[20]
The heat conductive sheet according to [19], wherein the mass change rate obtained by the following formula is less than 1.0%.
Mass change rate (%) = (W2-W1) / W1 × 100
W1: Mass of the heat-conducting sheet in a dry state after being dried in an environment of 120 ° C. for 2 hours W2: Moisture absorption after the heat-conducting sheet in a dry state is placed in an environment of 85 ° C. and 85 RH% for 24 hours. Mass of heat conductive sheet in state [21]
A device with a heat conductive layer having a device and a heat conductive layer including the heat conductive sheet according to [19] or [20] arranged on the device.

According to the present invention, it is possible to provide a curable composition that provides a heat conductive material having excellent heat conductivity and heat resistance.
Further, according to the present invention, it is possible to provide a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer relating to the curable composition.

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

Further, in the present specification, the description of "(meth) acryloyl group" means "either one or both of acryloyl group and methacryloyl group". Further, the description of "(meth) acrylamide group" means "either one or both of an acrylamide group and a methacrylamide group". The description "(meth) acrylic" means "either one or both of acrylic and methacrylic".

In the present specification, the acid anhydride group may be a monovalent group or a divalent group. When the acid anhydride group represents a monovalent group, a substitution obtained by removing an arbitrary hydrogen atom from an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. The group is mentioned. When the acid anhydride group represents a divalent group, the group represented by * -CO-O-CO- * is intended (* represents a bond position).

In the present specification, for substituents and the like that do not specify substitution or non-substitution, if possible, further substituents (for example, a group of substituents described later) are added to the groups as long as the desired effect is not impaired. Y) may be possessed. For example, the notation "alkyl group" means a substituted or unsubstituted alkyl group (an alkyl group which may have a substituent) as long as the desired effect is not impaired.
Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents in the case of "may have a substituent" are not particularly limited. Examples of the number of substituents include one or two or more. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and a group selected from the following 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 atoms (-F, -Br, -Cl, -I, etc.), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate base groups, anhydrous carboxylic acid groups, cyanate ester groups, unsaturated polymerizable groups, epoxy groups, oxetanyl Group, aziridinyl group, thiol group, isocyanate group, thioisocyanate group, aldehyde group, alkoxy group, allyloxy group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, N-alkylamino group, N, N-dialkylamino Group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N -Dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxi group, acylthio group, acylamino group, N-alkylacylamino group, N -Arylacylamino group, ureido group, N'-alkyl ureido group, N', N'-dialkyl ureido group, N'-aryl ureido group, N', N'-diaryl ureido group, N'-alkyl-N' -Allyl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl ureido group, N', N'-dialkyl-N-alkyl Ureid group, N', N'-dialkyl-N-aryl ureido group, N'-aryl-N-alkyl ureido group, N'-aryl-N-aryl ureido group, N', N'-diaryl-N-alkyl Ureid group, N', N'-diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl ureido group, N'-alkyl-N'-aryl-N-aryl ureido group, alkoxy Carbonylamino group, allyloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-allyloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N- Allyloxycarbonylamino group, formyl group, acyl group, alkoxycarbonyl group, allyloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diaryl Carbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO _3H ) and its conjugated base group, alkoxysulfonyl group, aryloxysulfonyl. Group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfina Moil group, sulfamoyl group, N-alkyl sulfamoyl group, N, N-dialkyl sulfamoyl group, N-aryl sulfamoyl group, N, N-diaryl sulfamoyl group, N-alkyl-N-arylsul Famoyl group, N-acylsulfamoyl group and its conjugated base group, N-alkylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonylsulfamoyl group ( -SO ₂ NHSO ₂ (aryl)) and its conjugated bases, N-alkylsulfonylcarbamoyl groups (-CONHSO ₂ (alkyl)) and its conjugated bases, N-arylsulfonylcarbamoyl groups (-CONHSO ₂ (aryl)) and Its conjugated base group, alkoxysilyl group (-Si (Oalkyl) ₃ ), aryloxysilyl group (-Si (Oaryl) ₃ ), hydroxysilyl group (-Si (OH) ₃ ) and its conjugated base group, phosphono group ( -PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (-PO ₃ (alkyl) ₂ ), diarylphosphono group (-PO ₃ (aryl) ₂ ), alkylarylphosphono group (-PO ₃ (-PO 3) Alkyl)), monoalkylphosphono groups (-PO ₃ H (alkyl)) and their conjugated base groups, monoarylphosphono groups (-PO ₃ H (aryl)) and their conjugated base groups, phosphonooxy groups ( -OPO ₃ H ₂ ) and its conjugate base group, dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (- OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugate base group, monoarylphospho Nooxy group (-OPO _3H (aryl)) and its conjugated base group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group, and alkyl group. Further, each of the above-mentioned groups may further have a substituent (for example, one or more groups among the above-mentioned groups), if possible. For example, an aryl group which may have a substituent is also included as a group selectable from the substituent group Y.
When the group selected from the substituent group Y has a carbon atom, the number of carbon atoms of the group is, for example, 1 to 20.
The number of atoms other than the hydrogen atom of the group selected from the substituent group Y is, for example, 1 to 30.
Further, these substituents may or may not form a ring by bonding with each other or with a group to be substituted, if possible. For example, the alkyl group (or the alkyl group portion in a group containing an alkyl group as a partial structure such as an alkoxy group) may be a cyclic alkyl group (cycloalkyl group) and has one or more cyclic structures as a partial structure. It may be an alkyl group.

[Composition]
The curable composition of the present invention (hereinafter, also simply referred to as “composition”) is one or both of a phenol compound, a maleimide compound having one or more maleimide groups, and a cyanate compound having one or more cyanate groups. And inorganic substances.
In addition, the above-mentioned inorganic substances include inorganic nitrides.
Maleimide compounds having one or more maleimide groups and cyanate compounds having one or more cyanate groups are also collectively referred to as "specific compounds".

The mechanism by which the composition of the present invention solves the problem of the present invention with the above-mentioned constitution is not always clear, but the present inventors speculate as follows.
First, the composition of the present invention contains an inorganic nitride having excellent thermal conductivity as an inorganic substance.
Further, the organic component includes a phenol compound and a specific compound. The specific compound in the composition can react with the phenol compound to form a heat conductive material (cured product) containing an inorganic nitride, and the polymer structure of such a heat conductive material has a high density, and the heat conduction of the heat conductive material is high. It is presumed that the improvement of the property and the heat resistance (Tg) could be realized.
Further, as described later, the composition may also contain an epoxy compound, and in such a case, the heat conductivity and heat resistance (Tg) of the heat conductive material are more excellent. This is because the polymer structure generated by the reaction of the phenol compound with the specific compound and the polymer structure generated by the reaction of the phenol compound with the epoxy compound form an IPN structure (interpenetrating network structure), and further, epoxy. It is presumed that the hydroxyl group generated from the group undergoes a cross-linking reaction with a specific compound (reaction between the hydroxyl group derived from the epoxy group and the double bond of the maleimide group, etc.) to form a denser polymer structure.
In addition, since a denser polymer structure is formed in the heat conductive material, it becomes difficult for water to penetrate into the heat conductive material and moisture absorption is suppressed. In addition, it is configured when the heat conductive material is exposed to high temperature. It is also suppressed that the components are thermally decomposed to generate volatile small molecules in the heat conductive material. As a result, even when the heat conductive material is placed at a high temperature, it is suppressed that the volatile components are vaporized from the heat conductive material and the adhesiveness is lowered, and the solder heat resistance of the heat conductive material is further improved. Has been done.
Further, the heat conductive material formed from the composition of the present invention has good insulating properties.
Hereinafter, the effect of the present invention is that at least one of the heat conductivity, heat resistance, insulating property, hygroscopicity suppressing property, and solder heat resistance of the heat conductive material formed by using the composition of the present invention is excellent. Is also said to be excellent.

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

[Phenol compound]
The composition of the present invention comprises a phenolic compound.
The phenol compound is a compound having 1 or more (preferably 2 or more, more preferably 2 to 10) hydroxyl groups (phenolic hydroxyl groups) directly bonded to the aromatic ring group.
Above all, the phenol compound preferably has a triazine skeleton.
By "having a triazine skeleton", a phenol compound means having one or more (for example, 1 to 5) triazine ring groups in the compound.

The phenol compound is preferably a compound represented by the general formula (Z).

In the above general formula (Z), when a plurality of groups represented by the same reference numeral are present, the plurality of groups represented by the same reference numeral may be the same or different, unless otherwise specified. ..

In the general formula (Z), E ¹ to E ⁶ independently represent a single bond, -NH-, or -NR-.
R represents a substituent. Examples of the substituent represented by R include a linear or branched alkyl group having 1 to 5 carbon atoms.
Independently, E ¹ to E ⁶ are preferably -NH- or -NR-, and more preferably -NH-.

In the general formula (Z), B ¹ represents a single bond or a k + 1 valent organic group.
B ² represents a single bond or an l + 1 valent organic group.
B ³ represents a single bond or m + 1 valent organic group.
B ⁴ represents a single bond or n + 1 valent organic group.
The values of k, l, m, and n in the above-mentioned k + 1-valent organic group, l + 1-valent organic group, m + 1-valent organic group, and n + 1-valent organic group are specified in the general formula (Z). , K, l, m, and n.
When r is 2 or more and the values of a plurality of existing m are different, the value of m in the m + 1 valent organic group represented by B ³ indicates the number of X ³ to which the B ³ is bonded. Is the same as the value of.

Examples of the organic group represented by B ¹ to B ⁴ include a group obtained by removing j hydrogen atoms from a hydrocarbon which may have a hetero atom having 1 to 20 carbon atoms. In addition, j means k + 1, l + 1, m + 1, or n + 1.
Here, as the above-mentioned hydrocarbon before removing j hydrogen atoms, for example, an aliphatic hydrocarbon having 1 to 20 carbon atoms which may have a substituent and a carbon which may have a substituent may be used. Examples thereof include one or more hydrocarbons selected from the group consisting of an aliphatic ring having the number of 3 to 20 and an aromatic ring having 3 to 20 carbon atoms which may have a substituent. Further, for the above 1 or more hydrocarbons, a group consisting of -O-, -S-, -CO-, -NR ^N- ( ^RN is a hydrogen atom or a substituent), and -SO _2- . One or more of the divalent linking groups selected from may be combined.
Examples of the aliphatic hydrocarbon 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 aromatic hydrocarbons having 6 to 20 carbon atoms and aromatic heterocycles having 3 to 20 carbon atoms.
Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring and the like, and examples of the aromatic heterocyclic ring having 3 to 20 carbon atoms include a furan ring, a pyrrole ring and a thiophene. Examples thereof include a ring, a pyridine ring, a thiazole ring, a carbazole ring, an indole ring, and a benzothiazole ring.

In the general 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 to 12, and more preferably an integer of 4 to 8.
The value of m in "r × m" is an average value of m that may exist in a plurality of values.
For k, l, m, and n, an integer of 0 to 5 is preferable, and an integer of 1 to 2 is more preferable, respectively.
For example, k is preferably 1 or more (for example, 1 to 2), l is preferably 1 or more (for example, 1 to 2), and m is preferably 1 or more (for example, 1 to 2). It is preferable that n is 1 or more (for example, 1 to 2).
When k is 0, B ¹ does not have X ¹ . When l is 0, B ² does not have X ² . If m is 0, then B ³ does not have X ³ . If n is 0, then B ⁴ does not have X ⁴ .
Further, 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 a divalent aromatic ring group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, and a substituent. Examples thereof include a divalent aliphatic ring group, -N ( ^RNA )-, -CO-, and a group combining these groups. R ^NA represents an organic group. The group exemplified as the divalent organic group may further have —O—, —S—, ^—N (RN) −, and a group in which these are combined.
^RN represents a substituent. Examples of the substituent represented by ^RN include a linear or branched alkyl group having 1 to 5 carbon atoms.
The aromatic ring group, the aliphatic hydrocarbon group, and the substituent that the aliphatic ring group may have include, for example, a linear or branched alkyl having 1 to 5 carbon atoms. The group etc. can be mentioned.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms and a divalent aromatic heterocyclic group having 3 to 20 carbon atoms.
Examples of the aromatic ring constituting the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a monocyclic aromatic ring such as a benzene ring; a naphthalene ring, and a polycyclic aromatic ring such as an anthracene ring; Examples of the aromatic heterocycle constituting a divalent aromatic heterocyclic group having 3 to 20 carbon atoms include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, and a monocycle such as a thiazole ring. Formula aromatic rings; polycyclic aromatic rings such as benzothiazole rings, carbazole rings, and indole rings; and the like.
As the divalent aromatic ring group as L, a group obtained by removing two hydrogen atoms from the above example can be mentioned.

Examples of the divalent aliphatic hydrocarbon group include an alkylene group having 1 to 12 carbon atoms, and specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and a methyl group. Examples thereof include a hexylene group and a heptylene group.

Examples of the aliphatic ring constituting the divalent aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a norbornane ring, and an adamantane ring.
As the aliphatic ring group as L, a group obtained by removing two hydrogen atoms from the above example can be mentioned.

A divalent aromatic ring group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, and a divalent aliphatic ring group which may have a substituent. Or, as a group in which -O-, -S-, -NR ^N- or -CO- is combined, not only a divalent linking group consisting of two or more of these, but also a group of the same type (for example, an example). It may be a divalent linking group in which two or more aromatic ring groups) are combined via a single bond.

In the present invention, it is preferable that both ends of L are carbon atoms from the viewpoint that the heat conductivity of the heat conductive material is more excellent. The terminal carbon atom may be part of a cyclic structure.
Further, in the present invention, from the viewpoint that the thermal conductivity of the heat conductive material is more excellent, L in the above general formula (P2) may have a divalent aromatic ring group or a substituent which may have a substituent. It is a divalent organic group having at least one selected from the group consisting of a divalent aliphatic ring group which may have and an alkylene group which may have a branch having 2 or more carbon atoms. It is preferable, and a divalent organic group having a divalent aromatic ring group which may have a substituent may be more preferable because the thermal conductivity is more excellent.

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

In the general 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" may be any aromatic ring group having one or more (for example, 1 to 4) hydroxyl groups (phenolic hydroxyl groups) directly bonded to the aromatic ring. The aromatic ring group may or may not have a substituent other than the hydroxyl group. The aromatic ring group may be monocyclic or polycyclic, and may have a heteroatom as a ring member atom. The number of ring member atoms of the aromatic ring group is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6.
The aromatic ring group is preferably a benzene ring group.
As the substituent that the aromatic ring group may have other than the hydroxyl group, a substituent having 1 to 6 carbon atoms is preferable, a hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a linear chain having 1 to 6 carbon atoms is more preferable. Alternatively, a branched alkyl group is more preferable.

In the general formula (Z), at least one of k X ¹ , l X ² , r × m X ³ , and n X ⁴ is a phenolic hydroxyl group. It is also preferable that the aromatic ring group has a substituent arranged at the ortho position of the phenolic hydroxyl group. The substituent may be present in only one of the ortho positions of the phenolic hydroxyl group, or may be present in both.
The value of m in "r × m" is an average value of m that may exist in a plurality of values.
The "substituted group arranged at the ortho position" is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and a linear or branched chain having 1 to 6 carbon atoms. Alkyl groups in the form are more preferable.
In other words, at least one (preferably 30% or more, more preferably 50) of the "aromatic ring groups having a phenolic hydroxyl group" represented by any of X ¹ to X ⁴ existing (k + l + r × m + n). % Or more, more preferably 65% or more, preferably 100% or less, more preferably 90% or less, still more preferably 80% or less) "a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group. It may represent "having an aromatic ring group".

Among the aromatic ring groups having a phenolic hydroxyl group represented by X ¹ to X ⁴ , the aromatic ring groups other than the "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" are It may or may not have a substituent other than a hydroxyl group (phenolic hydroxyl group).
Examples of 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" include a hydroxyphenyl group.
Of the (k + l + r × m + n) “aromatic ring groups having phenolic hydroxyl groups” represented by any of X ¹ to X ⁴ , at least one (for example, 1 to 2) is “phenolic hydroxyl group and phenol”. It is also preferable that it is an aromatic ring group other than the "aromatic ring group having a substituent arranged at the ortho position of the sex hydroxyl group".
Among the aromatic ring groups having phenolic hydroxyl groups represented by X ¹ to X ⁴ , there are also 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". It is considered that the symmetry of the compound as a whole is broken, the melting point of the compound is lowered, and the handleability of the semi-cured film formed from the composition is improved.

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

In the general formula (Z1), r represents an integer of 0 or more. r is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.
L represents a divalent organic group. The divalent organic group represented by L in the general formula (Z1) is, for example, the same as the divalent organic group represented by L in the general formula (Z1).
R ^Z represents a hydrogen atom or a substituent.
The substituent represented by ^RZ is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and a linear or linear group having 1 to 6 carbon atoms. It is more preferably a branched alkyl group.
At least one (preferably 30% or more, more preferably 50% or more, still more preferably 65% or more, preferably 90% or less, more preferably 80) of (3 + r) ^RZs present in the general formula (Z1). % Or less) may represent a substituent.
At least one (for example, 1 to 2) of R ^Z existing in (3 + r) in the general formula (Z1) may represent a hydrogen atom.
In the benzene ring group to which R ^z (preferably R ^z which is a substituent) and OH are bonded in the general formula (Z1), the above R ^z (preferably R ^z which is a substituent) is bonded to the above benzene ring group. It is also preferable that it exists in the para position with respect to NH.

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

In the general formula (Z2), R ^Z represents a hydrogen atom or a substituent.
It is also preferable that at least one of the two R ^Zs represents a substituent, and it is also preferable that both represent a substituent.
The substituent represented by ^RZ is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is even more preferable.
The alkyl group may be linear or branched. It is also preferable that the alkyl group is unsubstituted.
The two ^Rz in the general formula (Z2) may be the same or different from each other.

Other phenolic compounds include, for example, benzene polyols such as bisphenol A, F, S, AD, benzenediol or benzenetriol, biphenylaralkyl-type phenolic resins, phenol novolac resins, cresol novolac resins, and aromatic hydrocarbon formaldehyde resin modifications. Phenolic resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin, polyhydric phenol novolac resin synthesized from polyhydric hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolac resin , Naftorphenol co-condensed novolak resin, naphthol cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, alkoxy group-containing aromatic ring-modified novolak resin and the like are also preferable.

The molecular weight of the phenol compound is preferably 225 to 2000, more preferably 225 to 1000.
When the molecular weight has a molecular weight distribution, the molecular weight is a weight average molecular weight.

The hydroxyl group content of the phenol compound is preferably 2.0 mmol / g or more, more preferably 4.0 mmol / g or more. The upper limit is preferably 25.0 mmol / g or less, more preferably 10.0 mmol / g or less.
The hydroxyl group content is intended to be the number of hydroxyl groups (preferably phenolic hydroxyl groups) possessed by 1 g of the phenol compound.
In addition to the hydroxyl group, the phenol compound may or may not have an active hydrogen-containing group (carboxylic acid group or the like) capable of polymerizing with the epoxy compound. The lower limit of the active hydrogen content (total content of hydrogen atoms in hydroxyl groups, carboxylic acid groups, etc.) of the phenol compound is preferably 2.0 mmol / g or more, and more preferably 4.0 mmol / g or more. The upper limit is preferably 25.0 mmol / g or less, more preferably 10.0 mmol / g or less.

In addition to the phenol compound, the composition of the present invention may contain a compound having a group capable of reacting with the epoxy compound (also referred to as “other active hydrogen-containing compound”).
However, in the composition of the present invention, the mass ratio of the content of other active hydrogen-containing compounds to the content of the phenol compound is preferably 0 to 1, more preferably 0 to 0.1, and 0 to 0.05. Is more preferable.

The content of the phenol compound in the composition is preferably 3 to 90% by mass, more preferably 5 to 50% by mass, still more preferably 7 to 40% by mass, based on the total solid content of the composition.
The solid content is intended as a component forming a heat conductive material and does not contain a solvent. The component forming the heat conductive material referred to here may be a component whose chemical structure changes by reacting (polymerizing) when forming the heat conductive material. Further, if it is a component forming a heat conductive material, even if its property is liquid, it is regarded as a solid content.

[Epoxy compound]
It is also preferable that the composition of the present invention contains an epoxy compound.
An epoxy compound is a compound having at least one epoxy group (oxylanyl group) in one molecule.
The epoxy group is a group obtained by removing one or more hydrogen atoms (preferably one hydrogen atom) from the oxylan ring. If possible, the epoxy group may further have a substituent (a linear or branched alkyl group having 1 to 5 carbon atoms, or the like).

The number of epoxy groups contained in the epoxy compound is preferably 2 or more, more preferably 2 to 1000, and even more preferably 2 to 40 in one molecule.

The molecular weight of the epoxy compound is preferably 150 or more, more preferably 300 or more. The upper limit of the molecular weight is not limited, and for example, 100,000 or less is preferable, and 10,000 or less is more preferable.
When the molecular weight has a molecular weight distribution, the molecular weight is a weight average molecular weight.
In the present specification, the number average molecular weight and the weight average molecular weight are the 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 to 20.0 mmol / g, more preferably 5.0 to 15.0 mmol / g.
The epoxy group content is intended to be the number of epoxy groups contained in 1 g of the epoxy compound.
The epoxy compound also preferably has an aromatic ring group (preferably an aromatic hydrocarbon ring group).
The content of the epoxy compound having an aromatic ring group is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, based on the total epoxy compound.

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 the epoxy compound (which may be a liquid crystal epoxy compound) include a compound having at least a rod-like structure (rod-like compound) and a compound having at least a disk-like structure (disk-like compound). Can be mentioned.
Hereinafter, the rod-shaped compound and the disk-shaped compound will be described in detail.

(Stick compound)
Examples of the epoxy compound which is a rod-shaped compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenyls. Examples thereof include pyrimidines, phenyldioxans, trans, and alkenylcyclohexylbenzonitriles. Not only low molecular weight compounds as described above, but also high molecular weight compounds can be used. The polymer compound is a polymer compound obtained by polymerizing a rod-shaped compound having a small molecule reactive group.
Preferred rod-shaped compounds include rod-shaped compounds represented by the following general formula (XXI).
General formula (XXI): Q1 ^- L ¹¹¹ -A ¹¹¹ -L ¹¹³ -ML ¹¹⁴ -A ¹¹² -L ¹¹² -Q ²

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

In the general 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 independently -O-, -S-, -CO-, -NR ^112- , and -CO-O, respectively. -, -O-CO-O-, -CO-NR ^112- , -NR ¹¹² -CO-, -O-CO-, -CH ₂ -O-, -O-CH _2- , -O-CO-NR It is preferably a divalent linking group selected from the group consisting of ^112- , -NR ¹¹² -CO-O-, and -NR ¹¹² -CO-NR ^112- . The above R ¹¹² is an alkyl group or a hydrogen atom having 1 to 7 carbon atoms.
Among them, L ¹¹³ and L ¹¹⁴ are preferably —O— independently of each other.
L ¹¹¹ and L ¹¹² are preferably single bonds independently of each other.

In the general 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 heteroatoms such as non-adjacent oxygen and sulfur atoms. Of these, an alkylene group, an alkenylene group, or an alkynylene group having 1 to 12 carbon atoms is preferable. 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 divalent linking group may or may not have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, and bromine atom), a cyano group, a methyl group, and an ethyl group.
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 general formula (XXI), M represents a mesogen group, and examples of the mesogen group include known mesogen groups. Among them, the group represented by the following general formula (XXII) is preferable.
General formula (XXII):-(W ¹ -L ¹¹⁵ ) _n -W ^2-

In the general formula (XXII), W ¹ and W ² independently represent a divalent cyclic alkylene group, a divalent cyclic alkaneylene group, an arylene group, or a divalent heterocyclic group, respectively. L ¹¹⁵ represents a single bond or a divalent linking group. n represents an integer of 1 to 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 pyridazine-3,6-zyl. In the case of 1,4-cyclohexanediyl, it may be either a trans isomer or a cis structural isomer, or a mixture in any proportion. Of these, the transformer body is preferable.
W ¹ and W ² may each have a substituent. Examples of the substituent include the groups exemplified in the above-mentioned substituent group Y, and more specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), cyano group, and carbon. An alkyl group having a number of 1 to 10 (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (for example, a methoxy group, an ethoxy group, etc.), and a group having 1 to 10 carbon atoms. An acyl group (for example, a formyl group and an acetyl group, etc.), an alkoxycarbonyl group having 1 to 10 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.), and an acyloxy group having 1 to 10 carbon atoms (for example, an acyloxy group). Acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like can be mentioned.
When a plurality of W ^1s exist, the plurality of W ^1s may be the same or different from each other.

In the general formula (XXII), L ¹¹⁵ represents a single bond or a divalent linking group. Specific examples of the divalent linking group represented by L ¹¹⁵ include the above-mentioned divalent linking groups represented by L ¹¹¹ to L ¹¹⁴ , and examples thereof include -CO-O- and -O-CO-. , -CH ₂ -O-, and -O-CH _2- .
When a plurality of L ^115s are present, the plurality of L ^115s may be the same or different from each other.

The preferred skeleton of the basic skeleton of the mesogen group represented by the above general formula (XXII) is illustrated below. The above-mentioned mesogen groups may be substituted with a substituent in these skeletons.

Among the above skeletons, the biphenyl skeleton is preferable in that the obtained heat conductive material has more excellent heat conductivity.
The compound represented by the general formula (XXI) can be synthesized by referring to the method described in JP-A No. 11-513019 (WO97 / 00600).
The rod-shaped compound may be a monomer having a mesogen group described in JP-A No. 11-323162 and Japanese Patent No. 4118691.

Further, in the compound represented by the general formula (XXI), a compound in which one or both of "Q1 ^- ^L111- " and " ^-L112 - ^Q2 " are replaced with a diglycidylamino group is also preferable.

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

In the general formula ( ^E1 ), LE1 independently represents a single bond or a divalent linking group.
Of these, ^LE1 is preferably a divalent linking group.
The divalent linking groups are -O-, -S-, -CO-, -NH-, -CH = CH-, -C≡C-, -CH = N-, -N = CH-, -N = N-, an alkylene group which may have a substitution intention, or a group consisting of two or more of these is preferable, and -O-alkylene group- or -alkylene group-O- is more preferable.
The alkylene group may be linear, branched or cyclic, but a linear alkylene group having 1 to 2 carbon atoms is preferable.
A plurality of ^LE1s may be the same or different from each other.

In the general formula ( ^E1 ), LE2 are independently single-bonded, -CH = CH-, -CO-O-, -O-CO-, -C (-CH ₃ ) = CH-, -CH =. C (-CH ₃ )-, -CH = N-, -N = CH-, -N = N-, -C≡C-, -N = N ⁺ (-O ^- )-, -N ⁺ (-O" ^- ) = N-, -CH = N ⁺ (-O ^- )-, -N ⁺ ( ^-O- ) = CH-, -CH = CH-CO-, -CO-CH = CH-, -CH = C It represents (-CN)-or-C (-CN) = CH-.
Among them, ^LE2 is preferably single-bonded, -CO-O-, or -O-CO- independently of each other.
When there are a plurality of ^LE2s , the plurality of ^LE2s may be the same or different.

In the general formula (E1), ^LE3 is a 5-membered or 6-membered aromatic ring group or a 5-membered or 6-membered ring which may independently have a single bond or a substituent. Represents a non-aromatic ring group or a polycyclic group composed of these rings.
Examples of the aromatic ring group and the non-aromatic ring group represented by ^LE3 include 1,4-cyclohexanediyl group, 1,4-cyclohexendyl group and 1,4-phenylene which may have a substituent. Group, pyrimidin-2,5-diyl group, pyridine-2,5-diyl group, 1,3,4-thiadiazol-2,5-diyl group, 1,3,4-oxadiazole-2,5-diyl Examples thereof include a group, a naphthalene-2,6-diyl group, a naphthalene-1,5-diyl group, a thiophene-2,5-diyl group, and a pyridazine-3,6-diyl group. In the case of a 1,4-cyclohexanediyl group, it may be either a trans isomer or a cis structural isomer, or a mixture in any proportion. Above all, a transformer body is preferable.
Among them, ^LE3 is preferably a single bond, a 1,4-phenylene group, or a 1,4-cyclohexenediyl group.
The substituent of the group represented by ^LE3 is preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or an acetyl group, and more preferably an alkyl group (preferably 1 carbon number). preferable.
When a plurality of substituents are present, the substituents may be the same or different.
When there are a plurality of ^LE3s , the plurality of ^LE3s may be the same or different.

In the general formula (E1), pe represents an integer of 0 or more.
When pe is an integer of 2 or more, a plurality of ( ^-LE3 - ^LE2- ) may be the same or different from each other.
Among them, pe is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

In the general formula (E1), ^LE4 independently represents a substituent.
As the substituent, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or an acetyl group are preferable, and an alkyl group (preferably 1 carbon number) is more preferable.
A plurality of ^LE4s may be the same or different from each other. Further, when le described below is an integer of 2 or more, a plurality of ^LE4s existing in the same ( ^LE4 ) _le may be the same or different.

In the general formula (E1), le independently represents an integer of 0 to 4.
Among them, le is preferably 0 to 2 independently of each other.
A plurality of le's may be the same or different from each other.

Further, in the compound represented by the general formula ( ^E1 ), one or both of the two existing "epoxy groups-LE1-" are replaced with diglycidylaminoalkylene groups (preferably diglycidyl aminomethylene groups). Is also preferable.

It is also preferable that the rod-shaped compound has a biphenyl skeleton in that the obtained heat conductive material has better heat conductivity.
In other words, the epoxy compound preferably has a biphenyl skeleton, and the epoxy compound in this case is preferably a rod-shaped compound.

(Disc-shaped compound)
The epoxy compound, which is a disc-shaped compound, has a disc-shaped structure at least partially.
The disc-like structure has at least an alicyclic or aromatic ring. In particular, when the disk-shaped structure has an aromatic ring, the disk-shaped compound can form a columnar structure by forming a stacking structure by π-π interaction between molecules.
As a disk-shaped structure, specifically, Angew. Chem. Int. Ed. Examples thereof include the triphenylene structure described in 2012, 51, 7990-7793 or JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-002220 and JP-A-2010-2440338.

If a disk-shaped compound is used as the epoxy compound, a heat conductive material showing high heat conductivity can be obtained. The reason is that the rod-shaped compound can conduct heat only linearly (one-dimensionally), whereas the disk-shaped compound can conduct heat planarly (two-dimensionally) in the normal direction, so that the heat conduction path is It is thought that the number will increase and the thermal conductivity will improve.

The disk-shaped compound preferably has three or more epoxy groups. A cured product of a composition containing a disk-shaped compound having three or more epoxy groups tends to have a high glass transition temperature and high heat resistance.
The number of epoxy groups contained in the disk-shaped compound is preferably 8 or less, and more preferably 6 or less.

Specific examples of the disk-shaped compound include C.I. Destrade et al. , Mol. Crysr. Liq. Cryst. , Vol. 71, page 111 (1981); Chemical Society of Japan, Quarterly Review 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. Mol. Zhang et al. , J. Am. Chem. Soc. , Vol. In the compounds described in 116, page 2655 (1994), and Japanese Patent No. 4592225, compounds having at least one end (preferably three or more) as an epoxy group can be mentioned.
Examples of the disk-shaped compound include Angew. Chem. Int. Ed. Ends in the triphenylene structure described in 2012, 51, 7990-7793, and JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-002220 and JP-A-2010-240383. Examples thereof include compounds in which at least one (preferably three or more) of the above is used as an epoxy group.

As the disk-shaped compound, a compound represented by any of the following formulas (D1) to (D16) is preferable from the viewpoint of better thermal conductivity of the heat conductive material.
First, the equations (D1) to (D15) will be described, and then the equation (D16) will be described.
In the following formula, "-LQ" represents "-L-Q" and "QL-" represents "QL-".

In the formulas (D1) to (D15), L represents a divalent linking group.
From the viewpoint of better thermal conductivity of the thermally conductive material, L is independently an alkylene group, an alkaneylene group, an arylene group, -CO-, -NH-, -O-, -S-, and a combination thereof. It is preferable that the group is selected from the group consisting of, and two or more groups are selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O-, and -S-. More preferably, it is a combined group.
The alkylene group preferably has 1 to 12 carbon atoms. The number of carbon atoms of the alkenylene group is preferably 2 to 12. The arylene group preferably has 10 or less carbon atoms.
The alkylene group, alkenylene group, and arylene group may have a substituent (preferably an alkyl group, a halogen atom, a cyano, an alkoxy group, an acyloxy group, etc.).

An example of L is shown below. In the following example, the bond on the left side binds to the side of the central structure of the compound represented by any of the formulas (D1) to (D15) (hereinafter, also simply referred to as "central ring"), and the bond on the right side. Combines with Q.
AL means an alkylene group or an alkenylene group, and AR means an arylene group.
The alkylene group represented by AL may be linear or branched, and has, for example, 1 to 12 carbon atoms. The alkenylene group represented by AL may be linear or branched, and has, for example, 2 to 12 carbon atoms. The arylene group represented by AR may be monocyclic or polycyclic, and the number of ring member atoms is preferably 6 to 12.

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 the formulas (D1) to (D15), Q independently represents a hydrogen atom or a substituent.
Examples of the substituent include the groups exemplified in the above-mentioned substituent group Y. More specifically, as the substituent, the above-mentioned reactive functional group, halogen atom, isocyanate group, cyano group, unsaturated polymerizable group, epoxy group, oxetanyl group, aziridinyl group, thioisocyanate group, aldehyde group, and Examples include sulfo groups.
However, when Q is a group other than the epoxy group, it is preferable that Q is stable with respect to the epoxy group.
In the formulas (D1) to (D15), one or more (preferably two or more) Qs represent an epoxy group. Above all, from the viewpoint of better thermal conductivity of the heat conductive material, it is preferable that all Qs represent epoxy groups.
The compounds represented by the formulas (D1) to (D15) preferably do not have -NH- from the viewpoint of the stability of the epoxy group.

Among the compounds represented by the formulas (D1) to (D15), the compound represented by the formula (D4) is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material. In other words, the central ring of the disc-shaped compound is preferably a triphenylene ring.
As the compound represented by the formula (D4), the compound represented by the formula (XI) is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.

In formula (XI), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are independently * -X ¹¹ -L ¹¹ -P ¹¹ or * -X ¹² -L, respectively. ¹² -Y Represents ¹² .
Note that * represents the bonding position with the triphenylene ring.
Of 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 is preferable.
Above all, from the viewpoint of better thermal conductivity of the heat conductive material, one or more of R ¹¹ and R ¹² , one or more of R ¹³ and R ¹⁴ , and any one of R ¹⁵ and R ¹⁶ It is preferable that the number is * -X ¹¹ -L ¹¹ -P ¹¹ .
It is more preferable that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are all * -X ¹¹ -L ¹¹ -P ¹¹ . In addition, it is more preferred that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all the same.

X ¹¹ is independently single-bonded, -O-, -CO-, -NH-, -O-CO-, -O-CO-O-, -O-CO-NH-, -O-CO-. S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-, -NH-CO-O-, -NH-CO-NH-, -NH-CO-S- , -S-, -S-CO-, -S-CO-O-, -S-CO-NH-, or -S-CO-S-.
Among them, X ¹¹ independently have -O-, -O-CO-, -O-CO-O-, -O-CO-NH-, -CO-O-, -CO-NH-, and -NH. -CO- or -NH-CO-O- is preferable, and -O-, -O-CO-, -CO-O-, -O-CO-NH-, or -CO-NH- is more preferable. , -O-CO- or -CO-O- is even more preferred.

L ¹¹ independently represents a single bond or a divalent linking group.
Examples of divalent linking groups include -O-, -O-CO-, -CO-O-, -S-, -NH-, and alkylene groups (preferably 1 to 10 carbon atoms, 1 to 8 carbon atoms). Is more preferable, 1 to 7 is more preferable), an arylene group (the number of carbon atoms is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10), or a group consisting of a combination thereof. Can be mentioned.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptylene group.
Examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group and an anthrasenylene group, and a 1,4-phenylene group is preferable. ..

The alkylene group and the arylene 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 alkylene group and the arylene group are unsubstituted. Of these, the alkylene group is preferably unsubstituted.

Examples of −X ¹¹ − L ¹¹ − include L101 to L143, which are examples of L described above.

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

X ¹² is the same as X ¹¹ , 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 L101 to L143, which are examples of L described above.

Y ¹² is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. In, one or more methylene groups are substituted with -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -O-CO-, or -CO-O-. Represents a group.
One Y ¹² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Or a group in which two or more methylene groups are substituted with -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -O-CO-, or -CO-O-. In this case, one or more hydrogen atoms contained in Y ¹² may be substituted with halogen atoms.

For specific examples of the compound represented by the formula (XI), paragraph numbers 0028 to 0036 of JP-A-7-281028, paragraph numbers 0016 to 0018 of JP-A-7-306317 and JP-A-2005-156822 are provided. , Japanese Patent Laid-Open No. 2006-301614, paragraph numbers 0067 to 0072, and LCD Handbook (published by Maruzen Co., Ltd., 2000), pages 330 to 333, at least one at the end (preferably three or more). ) As an epoxy group.

The compound represented by the formula (XI) conforms to the methods described in JP-A-7-306317, JP-A-7-281028, JP-A-2005-156822, and JP-A-2006-301614. Can be synthesized.

Further, from the viewpoint of better thermal conductivity of the heat conductive material, the compound represented by the formula (D16) is also preferable as the disk-shaped compound.

In formula (D16), A ^2X , A ^3X , and A ^4X each independently represent −CH = or −N =. Above all, it is preferable that A ^2X , A ^3X , and A ^4X are all −CH = or all are −N =. That is, it is preferable that the 6-membered ring (central ring) including A ^2X , A ^3X , and A ^4X is a benzene ring or a triazine ring.
R ^17X , R ^18X , and R ^19X each independently represent * -X ^211X- (Z ^21X -X ^212X ) _n21X- L ^21X -Q. * Represents the position of connection with the central ring.
X ^211X and X ^212X are independently single-bonded, -O-, -CO-, -NH-, -O-CO-, -O-CO-O-, -O-CO-NH-, -O. -CO-S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-, -NH-CO-O-, -NH-CO-NH-, -NH-CO Represents —S—, —S—, —S—CO—, —S—CO—O—, —S—CO—NH—, or —S—CO—S—.
Z ^21X independently represents a 5- or 6-membered aromatic ring group or a 5-membered or 6-membered non-aromatic ring group, respectively.
L ^21X represents a single bond or a divalent linking group.
Q is synonymous with Q in the formulas (D1) to (D15), and the preferred conditions are also the same. In the formula (D16), at least one (preferably all) Q among the plurality of Qs present represents an epoxy group.
n21X represents an integer of 0 to 3. When n21X is 2 or more, a plurality of (Z ^21X -X ^212X ) may be the same or different.

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

In formula (XII), A ² , A ³ , and A ⁴ independently represent -CH = or -N =, respectively. Above all, it is preferable that A ² , A ³ and A ⁴ are all −CH = or all are −N =. That is, it is preferable that the 6-membered ring (central ring) including A ² , A ³ and A ⁴ is a benzene ring or a triazine ring.

R ¹⁷ , R ¹⁸ and R ¹⁹ are independently * -X ^211- (Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ²¹ or * -X ^221- (Z ²² -X ²²² ). Represents _n22 - ^Y22 . * Represents the position of connection with 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 viewpoint of better thermal conductivity of the heat conductive material, R ¹⁷ , R ¹⁸ and R ¹⁹ are all * -X ^211- (Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ²¹ . preferable.
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 are independently single-bonded, -O-, -CO-, -NH-, -O-CO-, -O-CO-O-, -O, respectively. -CO-NH-, -O-CO-S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-, -NH-CO-O-, -NH-CO Represents -NH-, -NH-CO-S-, -S-, -S-CO-, -S-CO-O-, -S-CO-NH-, or -S-CO-S-.
Among them, as X ²¹¹ , X ²¹² , X ²²¹ and X ²²² , single bond, -NH-, -O-, -CO-O-, or -O-CO- is preferable, respectively.

Z ²¹ and Z ²² 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 benzene ring group (1,4-). Examples thereof include a phenylene group and a 1,3-phenylene group), and an aromatic heterocyclic group.

The aromatic ring group and the 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 even 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 aromatic ring group and the non-aromatic ring group are unsubstituted. Further, as the 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.

In the formula, * represents a site that binds to X ²¹¹ or X ²²¹ . ** represents a site that binds to X ²¹² or X ²²² . A ⁴¹ and A ⁴² each independently represent a methine group or a nitrogen atom. ^X4 represents an oxygen atom, a sulfur atom, or an imino 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 nitrogen atoms. Further, ^X4 is preferably an oxygen atom.

When n21 and n22, which will be described later, are two or more, a plurality of (Z ²¹ -X ²¹² ) and (Z ²² -X ²²² ) may be the same or different from each other.

L ²¹ independently represents a single bond or a divalent linking group, and is synonymous with L ¹¹ in the above formula (XI). Examples of L ²¹ include -O-, -O-CO-, -CO-O-, -S-, -NH-, and an alkylene group (the number of carbon atoms is preferably 1 to 10 and more preferably 1 to 8). ~ 7 is more preferable), an arylene group (the number of carbon atoms is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10), or a group composed of a combination thereof is preferable.

When n22 is 1 or more, which will be described later, examples of ^−X212 ^−L21− include L101 to L143, which are examples of L in the above formulas (D1) to (D15). However, in this case, the bond on the left side of L101 to ^L143 binds to the side of the central structure of the compound (hereinafter, also simply referred to as “central ring”), and the bond on the right side binds to P21.

^P21 represents an epoxy group. The epoxy group may or may not have a substituent.

Each of Y ²² has a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic group having 1 to 20 carbon atoms. In the cyclic alkyl group, one or more methylene groups are -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -O-CO-, or -CO-. It represents a group substituted with O— and is synonymous with Y12 in the general formula ( ^XI ), and the preferred range is also the same.

n21 and n22 each independently represent an integer of 0 to 3, and an integer of 1 to 3 is preferable from the viewpoint of better thermal conductivity. Above all, when A ² , A ³ and A ⁴ are all −CH =, it is more preferable that n 21 and n 22 are independently integers of 2 to 3, respectively, and A ² , A ³ and A. When A ⁴ is all −N =, it is more preferable that n21 and n22 are 1 independently of each other.

Preferred examples of the disk-shaped compound include the following compounds.

In the following structural formula, R represents -X ²¹² -L ²¹ -P ²¹ .

For details and specific examples of the compound represented by the formula (XII), in the compounds described in paragraphs 0013 to 0077 of JP-A-2010-244033, at least one (preferably three or more) ends are epoxy. References can be made to the compound on which it is based, the contents of which are incorporated herein by reference.

The compound represented by the formula (XII) can be synthesized according to the methods described in JP-A-2010-244038, JP-A-2006-07692, and JP-A-2007-002220.

The disk-shaped compound is preferably a compound having a hydrogen-bonding functional group from the viewpoint of reducing the electron density, strengthening the stacking, and facilitating the formation of a columnar aggregate. Hydrogen-bonding functional groups include -O-CO-NH-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NH-CO-NH-, and -NH-CO-S. -Or-S-CO-NH- and the like can be mentioned.

(Other epoxy compounds)
In addition to the above-mentioned epoxy compound, the epoxy compound contains, for example, a phenolic hydroxyl group as an epoxy-containing group in the general formula (Z), the general formula (Z1), or the general formula (Z2) described in the description of the phenol compound. A compound represented by the general formula can also be used instead of.
The epoxy-containing group is a group that is the epoxy group itself, or a monovalent group that contains an epoxy group as a part.
The monovalent group containing the epoxy group as a part is a group having one or more (preferably 1 to 8) epoxy groups in the whole group.
The monovalent group containing the epoxy group as a part is preferably a group represented by "-(divalent hydrocarbon group) _M1- (-O-2-valent hydrocarbon group-) _M2 -epoxide group". In the above group, M1 represents 0 or 1. M2 represents an integer of 1 or more (preferably 1 to 10). Examples of the divalent hydrocarbon group in the above group include an alkylene group (preferably 1 to 6 carbon atoms), an alkenylene group (-CH = CH-, etc., preferably 2 to 6 carbon atoms) and an alkynylene group (-C). ≡C-etc., preferably 2 to 6 carbon atoms), an arylene group (such as a phenylene group, preferably 6 to 15 carbon atoms), and a group combining these. The divalent hydrocarbon group may or may not have a substituent, and the divalent hydrocarbon group may further have an epoxy-containing group as a substituent. The divalent hydrocarbon groups that may be present in a plurality thereof may be the same or different from each other.

Further, as the other epoxy compound, for example, an epoxy compound represented by the general formula (DN) can be mentioned.

In the general formula ( ^DN ), nDN represents an integer of 0 or more, and an integer of 0 to 5 is preferable, and 1 is more preferable.
^RDN represents a single bond or a divalent linking group. The divalent linking group includes -O-, -O-CO-, -CO-O-, -S-, an alkylene group (preferably 1 to 10 carbon atoms), and an arylene group (the carbon number is preferably 1 to 10). 6 to 20 is preferable), or a group composed of a combination thereof is preferable, an alkylene group is more preferable, and a methylene group is more preferable.

Examples of other epoxy compounds include epoxy compounds represented by the general formula (E2).
(V-) _4- UC (-W) _U (E2)

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

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

In the general formula (E2), V represents a substituent or a hydrogen atom having no epoxy group.
The above-mentioned substituent having no epoxy group is a substituent other than the epoxy group and does not contain an epoxy group as a part of the substituent.
Examples of the substituent having no epoxy group include a group selected from the substituent group Y, excluding an epoxy group and a group containing an epoxy group as a part.
The substituent having no epoxy group is preferably an alkyl group, and more preferably a linear or branched alkyl group. The alkyl group preferably has 1 to 5 carbon atoms.

In the general formula (E2), W represents an epoxy-containing group.
The epoxy-containing group is a group that is the epoxy group itself, or a monovalent group that contains an epoxy group as a part.
The monovalent group containing the epoxy group as a part is a group having one or more (preferably 1 to 8) epoxy groups in the whole group.
The monovalent group containing the epoxy group as a part is preferably a group represented by "-(divalent hydrocarbon group) _M1- (-O-2-valent hydrocarbon group-) _M2 -epoxide group". In the above group, M1 represents 0 or 1. M2 represents an integer of 1 or more (preferably 1 to 10). Examples of the divalent hydrocarbon group in the above group include an alkylene group (preferably 1 to 6 carbon atoms), an alkenylene group (-CH = CH-, etc., preferably 2 to 6 carbon atoms) and an alkynylene group (-C). ≡C-etc., preferably 2 to 6 carbon atoms), an arylene group (such as a phenylene group, preferably 6 to 15 carbon atoms), and a group combining these. The divalent hydrocarbon group may or may not have a substituent, and the divalent hydrocarbon group may further have an epoxy-containing group as a substituent. The divalent hydrocarbon groups that may be present in a plurality thereof may be the same or different from each other.
A plurality of Ws existing in the general formula (E2) may be the same or different from each other.

Examples of other epoxy compounds include compounds in which the epoxy group is fused. Examples of such a compound include 3,4: 8,9-diepoxybicyclo [4.3.0] nonane and the like.

Examples of other epoxy compounds include epoxy compounds represented by the general formula (E3).
Epoxy group-CH ₂ -O- (alkylene group-O) _X -CH ₂ -epoxy group (E3)
In the general formula (E3), X represents an integer of 1 or more, preferably an integer of 1 to 50, more preferably an integer of 1 to 15, and even more preferably an integer of 1 to 3.
The alkylene group in the general formula (E3) may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 3 carbon atoms, and even more preferably 2. When a plurality of the alkylene groups are present in the general formula (E3), the plurality of alkylene groups may be the same or different from each other.

Other epoxy compounds include, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and bisphenol AD type epoxy compounds, which are glycidyl ethers such as bisphenol A, F, S, and AD. Etc .; hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol AD type epoxy compound, etc .; phenol novolac type glycidyl ether (phenol novolak type epoxy compound), cresol novolak type glycidyl ether (cresol novolak type epoxy compound), bisphenol A Novolak type glycidyl ether etc .; Dicyclopentadiene type glycidyl ether (dicyclopentadiene type epoxy compound); Dihydroxypentadiene type glycidyl ether (dihydroxypentadiene type epoxy compound); Poly such as resorcinol or other dihydroxybenzene glycidyl ether Hydroxybenzene type glycidyl ether (polyhydroxybenzene type epoxy compound); benzenepolycarboxylic acid type glycidyl ester (benzenepolycarboxylic acid type epoxy compound); trisphenol methane type epoxy compound; phenoxy resin etc.; and epoxy on the side chain Acrylic resin having a group, and the like. A compound in which one or more of the glycidyl ether group and / or the glycidyl ester group in each of the above compounds is replaced with a diglycidylamino group or a diglycidylaminoalkylene group (diglycidylaminomethylene group, etc.) is used as the epoxy compound. You may.
Each of the above compounds may have a substituent. For example, the aromatic ring group, cycloalkane ring group, and / or alkylene group contained in each of the above compounds is other than the glycidyl ether group, the glycidyl ester group, the diglycidyl amino group, and / or the diglycidyl aminoalkylene group. It may have a substituent of.

The epoxy compound is a polyhydroxybenzene type glycidyl ether, a bisphenol F type glycidyl ether, an epoxy compound represented by the general formula (DN), a rod-shaped compound (preferably a rod-shaped compound having a biphenyl skeleton), or a disk-shaped compound (preferably). A disc-shaped compound having a biphenylene ring as the central ring, a disc-shaped compound having a triazine ring as the central ring, or a disc-shaped compound having a benzene ring as the central ring), a phenol novolac-type glycidyl ether, a phenoxy resin, and a general formula (E2). ), And one or more selected from the group consisting of the epoxy compound represented by the general formula (E3).
When the epoxy compound contains these compounds, the content thereof is more than 0% by mass and 100% by mass or less, preferably 30 to 100% by mass, more preferably 60 to 100% by mass, based on the total mass of the epoxy compound. It is preferable, 90 to 100% by mass is more preferable.

It is also preferable that the epoxy compound contains an epoxy compound having a viscosity at 25 ° C. of less than 1000 mPa · s (also referred to as “low viscosity epoxy compound”).
Further, in particular, when the composition contains the maleimide compound described later, it is preferable that the epoxy compound contains the above-mentioned low-viscosity epoxy compound.
When the epoxy compound contains a low-viscosity epoxy compound, flexibility is introduced into the semi-cured film formed from the composition to improve storage stability, and the semi-cured film after a certain period of time has passed since it was formed. Good handling. Such an improving effect is particularly remarkable when the composition contains a maleimide compound described later.
The viscosity of the low-viscosity epoxy compound at 25 ° C. is less than 1000 mPa · s, preferably 500 mPa · s or less, and more preferably 300 mPa · s or less. The lower limit of the viscosity is not particularly limited, but is, for example, 1 mPa · s or more.
The viscosity of the epoxy compound is a value obtained by measuring at 25 ° C. using RheoStress RS6000 (manufactured by Eiko Seiki Co., Ltd.) and reading the value 1 minute after the start of the measurement. The shear rate is 10 (1 / s).

When the epoxy compound contains a low-viscosity epoxy compound, the content of the low-viscosity epoxy compound is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and 60 to 100% by mass with respect to the total epoxy compounds. More preferred.
As the low-viscosity epoxy compound, for example, an epoxy compound having a predetermined viscosity among the above-mentioned epoxy compounds can be used, and more specifically, for example, bisphenol F type glycidyl ether, X is an integer of 1 to 13. Examples thereof include an epoxy compound represented by a general formula (E3) and a dihydroxybenzene type glycidyl ether.

[Relationship between phenol compounds and epoxy compounds]
In the composition of the present invention when an epoxy compound is contained, the phenol compound contains a phenol compound having a triazine skeleton (requirement 1), and the epoxy compound contains an epoxy compound having a triazine skeleton (requirement 2). It is preferable to meet at least one requirement.
The composition may satisfy only Requirement 1, only Requirement 2, or both Requirement 1 and Requirement 2.

By "having a triazine skeleton" of a phenol compound and an epoxy compound, it means that the compound has one or more (for example, 1 to 5) triazine ring groups.
Examples of the phenol compound having a triazine skeleton include the above-mentioned compound represented by the general formula (Z), the compound represented by the general formula (Z1), and the compound represented by the general formula (Z2). Be done.
Examples of the epoxy compound having a triazine skeleton include the above-mentioned compound represented by the formula (D16) in which A ^2X , A ^3X , and A ^4X are all −N =, formula (XII). In the compound represented by, A ² , A ³ and A ⁴ are all in the form of −N =, and are represented by the general formula (Z) in which the phenolic hydroxyl group is replaced with the epoxy-containing group. The compound is represented by a general formula in which the phenolic hydroxyl group is replaced with an epoxy-containing group in the general formula (Z1), and a general formula in which the phenolic hydroxyl group is replaced with an epoxy-containing group in the general formula (Z2). Examples include compounds.

When the phenol compound contains a phenol compound having a triazine skeleton (for example, when requirement 1 is satisfied), the content thereof is more than 0% by mass and 100% by mass or less with respect to the total mass of the phenol compound, and is 30 to 100. It is preferably by mass, more preferably 60 to 100% by mass, still more preferably 90 to 100% by mass. When the composition contains an epoxy compound and the epoxy compound contains an epoxy compound having a triazine skeleton (that is, when requirement 2 is satisfied), the content of the phenol compound having a triazine skeleton is out of the above preferable range. Is also preferable.
When the composition contains an epoxy compound and the above epoxy compound contains an epoxy compound having a triazine skeleton (that is, when requirement 2 is satisfied), the content thereof is more than 0% by mass and 100% based on the total mass of the epoxy compound. It is not more than mass%, preferably 30 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 90 to 100% by mass. When the phenol compound contains a phenol compound having a triazine skeleton (that is, when requirement 1 is satisfied), the content of the epoxy compound having a triazine skeleton may be outside the above preferable range.

When the composition contains an epoxy compound, it is also preferable that at least a part of the phenol compound and the epoxy compound is other than a compound having a triazine skeleton.
All or part of the phenol compound may be other than the compound having a triazine skeleton, and all or part of the epoxy compound may be other than the compound having a triazine skeleton.
When the composition contains an epoxy compound, the total content of the phenol compound having a triazine skeleton and the epoxy compound having a triazine skeleton is the total phenol compound and the total content from the viewpoint of adjusting the cross-linking density and further improving the effect of the present invention. With respect to the total content with the epoxy compound, it is preferably more than 0% by mass and less than 100% by mass, more preferably 1 to 90% by mass, still more preferably 5 to 80% by mass.

The total content of the epoxy compound and the phenol compound in the composition is preferably 3 to 90% by mass, more preferably 5 to 50% by mass, and 7 to 40% by mass with respect to the total solid content of the composition. Is more preferable.
The epoxy compound and / or the phenol compound may be used alone or in combination of two or more.

In the composition, the ratio of the total number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenol compound to the total number of epoxy groups contained in the epoxy compound (number of epoxy groups / number of hydroxyl groups) is usually used. It is 3/97 to 97/3, preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and even more preferably 45/55 to 55/45.
That is, the ratio of the content of the phenol compound to the epoxy compound in the composition is preferably such that the above-mentioned "number of epoxy groups / number of phenolic hydroxyl groups" is within the above range.

Further, in the composition, the equivalent ratio (may be active hydrogen derived from a phenolic hydroxyl group or active hydrogen of another active hydrogen-containing compound) between the epoxy group of the epoxy compound and the active hydrogen (may be active hydrogen derived from a phenolic hydroxyl group). The number of epoxy groups / number of active hydrogens) is usually 3/97 to 97/3, preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and 45/55 to 55 /. 45 is more preferred.

Further, in the composition, the ratio of the total number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenol compound to the total number of epoxy groups contained in the epoxy compound (number of epoxy groups / number of hydroxyl groups) is , 1.1 / 1.0 to 3.0 / 1.0, more preferably 1.2 / 1.0 to 2.0 / 1.0, and 1.3 / 1. It is more preferably 0 to 1.8 / 1.0. In other words, the ratio of the total number of epoxy groups contained in the epoxy compound (number of epoxy groups / number of hydroxyl groups) to the total number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenol compound is 1.1. It is preferably ~ 3.0, more preferably 1.2 to 2.0, and even more preferably 1.3 to 1.8.
Further, it is particularly preferable that the above ratio is within the above range when the composition contains the maleimide compound described later.
When the above ratio is equal to or higher than a predetermined value, flexibility is introduced into the semi-cured film formed from the composition to improve storage stability, and the handling property of the semi-cured film is improved even after a certain period of time has passed since the formation. Becomes good. When the above ratio is not more than a predetermined value, the heat resistance of the heat conductive material formed from the composition is more excellent. Such an improving effect is particularly remarkable when the composition contains a maleimide compound described later.

The composition may contain little or no epoxy compound. In this case, the ratio of the number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenol compound to the total number of epoxy groups contained in the epoxy compound (number of epoxy groups / number of hydroxyl groups) in the composition is. For example, it is 0/100 or more and less than 3/97 (preferably 0/100 or more and 1/99 or less (0 or more and less than 0.031, preferably 0 or more and 0.011 or less)).

[Specific compound]
The composition comprises a specific compound.
The specific compound is a general term for a maleimide compound having one or more maleimide groups and a cyanate compound having one or more cyanate groups.
That is, the composition comprises one or both of the maleimide compound and the cyanate compound.

In this specification, compounds having both a maleimide group and a cyanate group are classified as follows. That is, among the maleimide groups and cyanate groups of the above compound, if the number of maleimide groups is larger, the above compound is classified as a maleimide compound, and if the number of cyanate groups is larger, the above compound is classified as a cyanate compound. When the number of maleimide group and cyanate group is the same, the above compound is classified as a maleimide compound.

The total content of the specific compound is preferably 0.1 to 40% by mass, more preferably 1 to 25% by mass, still more preferably 3.5 to 15% by mass, based on the total solid content of the composition.
The total content of the specific compound is preferably 5 to 200% by mass, more preferably 10 to 180% by mass, still more preferably 20 to 160% by mass, based on the total content of the epoxy compound and the phenol compound. When the composition does not contain the epoxy compound, the total content means the content of the phenol compound alone.
It is also preferred that the composition comprises substantially only one of the maleimide compound and the cyanate compound. In this case, for example, the content of one of the maleimide compound and the cyanate compound is preferably more than 98% by mass and 100% by mass or less, preferably 99 to 100% by mass, based on the total mass of the specific compound. Is more preferable, and 99.9 to 100% by mass is further preferable.
When the composition contains both a maleimide compound and a cyanate compound, the mass ratio of the cyanate compound content to the maleimide compound content in the composition (the content mass of the cyanate compound / the content mass of the maleimide compound) is 2/98 to 98/2 is preferable, 70/30 to 70/30 is more preferable, and 40/60 to 60/40 is even more preferable.

<Maleimide compound>
The composition preferably contains at least a maleimide compound among the specific compounds.
A maleimide compound is a compound having one or more maleimide groups.

The number of maleimide groups contained in the maleimide compound is 1 or more, preferably 1 to 100, more preferably 2 to 10, and even more preferably 2.
The maleimide compound may be a high molecular weight compound or a low molecular weight compound.
For example, the molecular weight of the maleimide compound is preferably 100 to 3000, more preferably 200 to 2000, and even more preferably 300 to 1000.

The maleimide group contained in the maleimide compound is preferably a group represented by the following general formula (M).

In the general formula (M), * represents a bonding position.
X and Y each independently represent a hydrogen atom or a substituent.
Hydrogen atoms are preferable for X and Y independently of each other.

The maleimide compound is also preferably a compound having one or more (preferably 1 to 10) aromatic ring groups (benzene ring groups and the like).
Among them, the maleimide compound is preferably a compound represented by the following general formula (1).

In the general formula (1), m represents 0 or 1. m is preferably 1.
n represents 0 or 1. n is preferably 1.

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

In the general formula (1), L ¹ represents a divalent linking group.
Examples of the divalent linking group include an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S-), -SO _2- , and -NR. -(R is a hydrogen atom or an alkyl group), a divalent aliphatic hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group (-CH = CH-, etc.), an alkynylene group (-C≡C). -Etc.)), a divalent aromatic ring group (allylen group and a heteroarylene group), and a group combining these groups can be mentioned.
In the general formula (1), the number of carbon atoms of L1 is preferably ¹ or more, more preferably 1 to 100, and even more preferably 3 to 15.

Among them, L ¹ is preferably a group represented by "* ^p- (L ² -Ar) _k- * ^q ".
* ^Q represents the bond position on the side that directly bonds to the maleimide group, and * ^p represents the bond position on the opposite side.
k represents an integer of 1 or more, preferably 1 to 10, and more preferably 1.
L ² represents a single bond, -C (R ³ ) (R ⁴ )-, -O-, or -CO-, with -C (R ³ ) (R ⁴ )-preferably.
R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and an alkyl group (which may be linear or branched and has, for example, 1 to 10 carbon atoms) is preferable.
Ar represents an arylene group. The number of ring-membered atoms of the arylene group is preferably 6 to 15, and more preferably 6. When the arylene group has a substituent, the number thereof is preferably 1 to 4, more preferably 1 or 2. As the substituent that the arylene group may have, an alkyl group (which may be linear or branched and has, for example, 1 to 10 carbon atoms) is preferable. Examples of the structure in which Ar can be formed include a structure in which a benzene ring group bonded to R ¹ and R ² can be formed, which is specified in the general formula (1).
When a plurality of L ² and Ar exist, the plurality of L ² existing and the plurality of Ar existing may be the same or different from each other.

In the general formula (1) when n is 1, a maleimide group and a group represented by "-(L ¹ ) _m -maleimide group" are 2 on the benzene ring group bonded to R ¹ and R ² . The two groups may be arranged in the ortho position, the meta position, or the para position with each other. Among them, it is preferable that the above two groups are arranged at the meta position or the para position.

Among them, in the compound represented by the general formula (1), m represents 1, n represents 1, and the divalent linking group represented by L ¹ has 3 to 15 carbon atoms. preferable.

Only one kind of maleimide compound may be used, or two or more kinds may be used.
The content of the maleimide compound is preferably 0.1 to 40% by mass, more preferably 1 to 15% by mass, and the handleability of the semi-cured film formed from the composition is more preferable with respect to the total solid content of the composition. From an excellent point of view, 3.5 to 8% by mass is more preferable.
Further, from the viewpoint of more excellent thermal conductivity and / or insulating property of the obtained thermal conductive agent material, the content of the maleimide compound is 6% by mass or more (for example, 6) with respect to the total solid content of the composition. It is also preferable that it is ~ 12% by mass).
When the composition contains an epoxy compound, the content of the maleimide compound is, for example, 1 to 200% by mass, preferably 5 to 100% by mass, and 10 to 70% by mass, based on the total content of the epoxy compound and the phenol compound. The mass% is more preferable, and 20 to 60% by mass is further preferable.
The content of the maleimide compound is, for example, 1 to 500% by mass, preferably 20 to 300% by mass, more preferably 50 to 200% by mass, still more preferably 70 to 130% by mass, based on the content of the phenol compound. ..

<Cyanate compound>
The composition preferably contains at least a cyanate compound among the specific compounds.
A cyanate compound is a compound having one or more cyanate groups (-OCN).

The number of cyanate groups contained in the cyanate compound is 1 or more, preferably 1 to 100, and more preferably 2 to 50.
The cyanate compound may be a high molecular weight compound or a low molecular weight compound.
For example, the molecular weight of the cyanate compound is preferably 100 to 3000, more preferably 200 to 2000, and even more preferably 300 to 1000.

The cyanate compound is also preferably a compound having one or more (preferably 1 to 10) aromatic ring groups (benzene ring groups and the like).
Among them, the cyanate compound is preferably a compound represented by the following general formula (2).

In the general formula (2), nc represents an integer of 0 or more.
The nc is preferably an integer of 0 to 100.

In the general formula (2), L ^c represents a single bond or a divalent linking group.
Examples of the divalent linking group include an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S-), -SO _2- , and -NR. -(R is a hydrogen atom or an alkyl group), a divalent aliphatic hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group (-CH = CH-, etc.), an alkynylene group (-C≡C). -Etc.)), a divalent aromatic ring group (allylen group and a heteroarylene group), and a group combining these groups can be mentioned.
Among them, the divalent linking group is preferably an alkylene group, a cycloalkylene group, or a thioether group.
The alkylene group may be linear or branched, and the number of carbon atoms is preferably 1 to 8. Among them, the alkylene group is preferably —C ( ^RA ) ( ^RB ) —. ^RA and ^RB each independently represent a hydrogen atom, a halogen atom, or an alkyl group. The alkyl group may be linear or branched, and the number of carbon atoms is preferably 1 to 3. As the substituent that the alkyl group may have, a halogen atom is preferable, and a fluorine atom is more preferable. The alkyl group is also preferably a perfluoroalkyl group.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms. As the cycloalkylene group, a tetrahydrodicyclopentadiene ring group is preferable.
In the general formula (2), when a plurality of L ^cs are present, the plurality of L ^cs may be the same or different.

In the general formula (2), ^Arc represents an aromatic ring group.
The aromatic ring group may be monocyclic or polycyclic, and the number of ring member atoms is preferably 5 to 20.
The aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and an aromatic hydrocarbon ring group is preferable.
Of these, the aromatic ring group is preferably a benzene ring group.
The aromatic ring group may have one or more substituents (for example, 1 to 4) in addition to the cyanate group (—OCN) specified in the general formula (2). As the substituent, an alkyl group (which may be linear or branched, preferably having 1 to 3 carbon atoms) is preferable.
Further, a cyanate group may be further provided as a substituent other than the cyanate group (—OCN) specified in the general formula (2).
In the general formula (2), when a plurality of ^Arcs are present, the plurality of ^Arcs may be the same or different.

As the cyanate compound, a prepolymerized product may be used, and for example, a prepolymerized product of the compound represented by the above-mentioned general formula (2) may be used.
The prepolymerized product referred to here is a cyanate compound in a prepolymer state in which cyanate compounds (preferably compounds represented by the above general formula (2)) are polymerized to a certain extent and then the reaction is stopped. ..

As the cyanate compound, for example, a compound exemplified below and a prepolymer product of one or more compounds selected from the compounds exemplified below can be used.
In the following examples, n represents an integer of 1 or more.

As the cyanate compound, a commercially available product may be used.
Examples of commercially available products include CYTESTER TA, TA-100, TA-1500, P-201 (all manufactured by Mitsubishi Gas Chemical Company), and AROCY XU371 (manufactured by Huntsman).

Only one type of cyanate compound may be used, or two or more types may be used.
The content of the cyanate compound is preferably 0.1 to 40% by mass, more preferably 1 to 15% by mass, still more preferably 3.5 to 10% by mass, based on the total solid content of the composition.
When the composition contains an epoxy compound, the content of the cyanate compound is, for example, 1 to 300% by mass, preferably 5 to 250% by mass, and 10 to 200% by mass, based on the total content of the epoxy compound and the phenol compound. The mass% is more preferable, and 20 to 150% by mass is further preferable.
The content of the cyanate compound is, for example, 1 to 600% by mass, preferably 20 to 500% by mass, more preferably 50 to 400% by mass, still more preferably 70 to 300% by mass, based on the content of the phenol compound. ..

[Inorganic substances]
The composition comprises an inorganic substance.
As the inorganic substance, only one kind may be used, or two or more kinds may be used.
As the inorganic substance, any inorganic substance conventionally used for the inorganic filler of the heat conductive material may be used.
Further, the above-mentioned inorganic substance contains at least an inorganic nitride (preferably boron nitride).
The inorganic substance may further contain an inorganic oxide (preferably aluminum oxide) in addition to the inorganic nitride.

The shape of the inorganic substance is not particularly limited, and may be in the form of particles, a film, or a plate. Examples of the shape of the particulate inorganic substance include rice granules, spherical shape, cube shape, spindle shape, scale shape, agglomerate shape, and indefinite shape.

The size of the inorganic substance is not particularly limited, but the average particle size of the inorganic substance is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, in that the dispersibility of the inorganic substance is more excellent. The lower limit is not particularly limited, but in terms of handleability, 10 nm or more is preferable, and 100 nm or more is more preferable.
As the average particle size of the inorganic substance, the catalog value is adopted when a commercially available product is used. If there is no catalog value, as the method for measuring the average particle size, 100 inorganic substances are randomly selected, the particle size (major axis) of each inorganic substance is measured, and the arithmetic is performed. Calculate on average.

In that the heat conductive material is more excellent in heat conductivity, the composition is an inorganic substance (preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride) having an average particle size of 20 μm or more (preferably 30 μm or more). , More preferably, boron nitride, particularly preferably aggregated boron nitride).

Examples of the inorganic nitride, which is a form of an inorganic substance, 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), Lantern Nitride (La N), Lithium Nitride (Li ₃ N) ), Magnesium Nitride (Mg ₃ N ₂ ), Molybdenum Nitride (Mo ₂ N), Nitride (NbN), Tantal Nitride (TaN), Titanium Nitride (TiN), Tungsten Nitride (W ₂ N), Tungsten Nitride (WN ₂ ) ), Ittrium nitride (YN), zirconium nitride (ZrN) and the like.
As the above-mentioned inorganic nitride, only one kind may be used, or two or more kinds may be used.
The inorganic nitride preferably contains an aluminum atom, a boron atom, or a silicon atom, more preferably aluminum nitride, boron nitride, or silicon nitride, and even more preferably aluminum nitride or boron nitride. It is particularly preferable to contain boron nitride. Most preferably, the boron nitride contains at least aggregated boron nitride having an average particle size of 20 μm or more.
The content of the inorganic nitride (preferably boron nitride and / or aluminum nitride, more preferably aggregated boron nitride having an average particle size of 20 μm or more) in the inorganic substance is 10 to 100% by mass with respect to the total mass of the inorganic substance. Is preferable, 40 to 100% by mass is more preferable, and 60 to 100% by mass is further preferable.

Examples of the inorganic oxide, which is a form of an inorganic substance, include zirconium oxide (ZrO ₂ ), titanium oxide (TIO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and 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 ), Tantal oxide (Ta ₂ O ₅ ), Tungsten oxide (WO ₃ , W ₂ O ₅ ), Lead oxide (PbO, PbO ₂ ) , Bismus 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 ), ruthenium oxide (RuO ₂ ) and the like can be mentioned.
It is also preferable that the inorganic oxide is different from the inorganic ion scavenger described later.
Only one kind of inorganic oxide may be used, or two or more kinds may be used.
The inorganic oxide is preferably titanium oxide, aluminum oxide (alumina), or zinc oxide, and more preferably aluminum oxide.
The inorganic oxide may be an oxide produced by oxidizing a metal prepared as a non-oxide in an environment or the like.

The inorganic substance may contain an inorganic substance (inorganic ion scavenger) corresponding to the ion scavenger.
Examples of the inorganic ion trapping agent include a cation adsorbent that captures cations by ion exchange, an anion adsorbent that captures anions by ion exchange, and an anion adsorbent that captures both cations and anions by ion exchange. Examples thereof include inorganic ion adsorbents such as both ion trapping agents.

Examples of the inorganic ion scavenger include an inorganic substance (preferably a composite inorganic substance) containing one or more (preferably two or more) selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, and magnesium. Can be mentioned. Examples of the inorganic substance (preferably a composite inorganic substance) containing one or more of the above (preferably two or more) include an oxide (preferably a composite oxide), an oxidative hydrate (preferably a composite oxidative hydrate), and an oxide. , Hydroxides (preferably composite hydroxides).
In addition, as the inorganic ion trapping agent, a composite inorganic substance (composite oxide, composite oxidation) of one or more selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, and magnesium and aluminum is used. Hydrate, composite hydroxide, etc.) can also be mentioned.
Examples of the composite oxide include aluminum oxide / magnesium oxide solid solution.

The inorganic ion trapping agent which is a composite is two or more kinds of oxides (composite oxides) and oxidative hydrates (composite oxide waters) selected from the group consisting of antimony, bismuth, zirconium, magnesium, and aluminum. Japanese products) or hydroxides (composite hydroxides) are preferable.
Among them, the inorganic ion trapping agent is a two-component composite of magnesium, aluminum, and zirconium (composite oxide, composite oxidative hydrate, composite hydroxide, etc.), bismuth, and zirconium. Substances (composite oxides, composite oxidative hydrates, composite hydroxides, etc.), two-component composites of bismuth and antimony (composite oxides, composite oxidative hydrates, composite hydroxides, etc.), Alternatively, a composite containing magnesium and aluminum (composite oxide, composite oxidative hydrate, composite hydroxide, etc.) is preferable, and a two-component composite of bismuth and zirconium or a two-component composite of magnesium and aluminum. Complexes are more preferred.
When the inorganic ion trapping agent contains two or more kinds of metal atoms, the inorganic ion trapping agent contains two kinds of metal atoms in which the content of the inorganic ion trapping agent with respect to all metal atoms is in the range of 1 to 99 mol%. It is preferable to include the above (for example, 2 to 4 types), and 2 or more types (for example, 2 to 4 types) of metal atoms having an content of the inorganic ion trapping agent with respect to all metal atoms in the range of 5 to 95 mol% are contained. Is more preferable.

The content of the inorganic ion scavenger is preferably 0.01 to 40% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.2 to 10% by mass, based on the total inorganic substances.

It is also preferable that the inorganic substance in the composition is substantially composed of only the inorganic nitride and the inorganic ion adsorbent. For example, the total content of the inorganic nitride and the inorganic ion adsorbent is higher than that of the total inorganic substance. , 98 to 100% by mass, more preferably 99.95 to 100% by mass, and particularly preferably 99.995 to 100% by mass.

The inorganic material contained in the composition (preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride, further preferably boron nitride and / or aluminum nitride) has a substantially average particle size of 20 μm or more (preferably 30 μm). It is also preferable that only the inorganic substances of the above) are used. The fact that the inorganic substances are substantially only inorganic substances having an average particle size of 20 μm or more means that the content of the inorganic substances having an average particle size of 20 μm or more is more than 99% by mass with respect to the total mass of the inorganic substances.

Further, the inorganic substance preferably has an inorganic substance having a different average particle size, for example, both an inorganic substance X having an average particle size of 20 μm or more and an inorganic substance Y having an average particle size of less than 20 μm. It is also preferable to include it.
The average particle size of the inorganic substance X is preferably 20 to 300 μm, more preferably 30 to 200 μm. The average particle size of the inorganic substance Y is preferably 1 nm or more and less than 20 μm, and more preferably 10 nm or more and 15 μm or less.
The inorganic substance X is preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride, and even more preferably boron nitride. It is also preferable that the inorganic substance X is in the form of agglomerates.
The inorganic substance Y is preferably an inorganic nitride or an inorganic oxide, more preferably boron nitride or aluminum oxide. It is also preferable that the inorganic substance Y is not in the form of agglomerates.
As the inorganic substance X and the inorganic substance Y, one kind may be used alone, or two or more kinds may be used.
The mass ratio of the content of the inorganic substance X to the content of the inorganic substance Y (content of the inorganic substance X / content of the inorganic substance Y) is preferably 50/50 to 99/1, and 60/40 to 95/5. Is more preferable, and 60/40 to 90/10 is even more preferable.

Inorganic substances (particularly boron nitride) may be surface-treated. The surface treatment is intended to be a treatment different from the surface modification using a surface modifier described later.
By performing such a treatment, a functional group is introduced on the surface of the inorganic substance, and the inorganic substance easily interacts with a phenol compound, an epoxy compound, and / or a surface modifier described later, and is formed as a heat conductive material. It is considered that the thermal conductivity and peel strength of the above are further improved.
The surface treatment includes, for example, plasma treatment (vacuum plasma treatment, atmospheric pressure plasma treatment, aqua plasma treatment, etc.), ultraviolet irradiation treatment, corona treatment, electron beam irradiation treatment, ozone treatment, firing treatment, flame treatment, and Oxidizing agent treatment and the like can be mentioned. The oxidizing agent treatment may be carried out under acidic conditions or basic conditions (pH 12 or higher, etc.).

The content of the inorganic substance in the composition is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on the total solid content of the composition. .. The upper limit is less than 100% by mass, preferably 95% by mass or less, and more preferably 83% by mass or less.

[Surface modifiers, surface modifiers]
The composition of the present invention may further contain a surface modifier as a component different from the above-mentioned components.
The surface modifier is a component that surface-modifies the above-mentioned inorganic substances.
As used herein, "surface modification" means a state in which an organic substance is adsorbed on at least a part of the surface of the inorganic substance. The form of adsorption is not particularly limited, and may be in a bonded state. That is, the surface modification also includes a state in which an organic group obtained by desorption of a part of an organic substance is bonded to the surface of the inorganic substance. The bond may be any bond such as a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metal bond. The surface modification may be made to form a monomolecular film on at least a part of the surface. The monolayer is a monolayer formed by chemisorption of organic molecules and is known as Self-Assembled MonoLayer (SAM). In addition, in this specification, the surface modification may be only a part of the surface of an inorganic substance, or may be the whole.

As used herein, the "surface-modified inorganic substance" is an inorganic substance that has been surface-modified with a surface-modifying agent. That is, the surface-modifying inorganic substance is a material containing the inorganic substance and the surface modifying agent adsorbed on the surface of the inorganic substance.
That is, in the composition of the present invention, the inorganic substance may constitute a surface-modifying inorganic substance together with the surface modifying agent adsorbed on the surface of the inorganic substance.
Further, in the present invention, the composition may contain an inorganic substance and a surface modifying agent by containing the surface-modifying inorganic substance.
The inorganic substance in the composition may be partially or wholly composed of the surface-modifying inorganic substance together with the surface-modifying agent. For example, in the composition, there may be an inorganic substance that constitutes a surface-modified inorganic substance of some inorganic substances and at the same time does not participate in the composition of the surface-modified inorganic substance.
A part or all of the surface modifier in the composition may constitute a surface-modifying inorganic substance together with the inorganic substance. For example, in the composition, some surface modifiers may constitute the surface-modifying inorganic substance, and at the same time, a surface modifier which is not involved in the composition of the surface-modifying inorganic substance may be present.
Among them, the composition is a surface-modified inorganic nitride (preferably boron nitride, more preferably agglomerated boron nitride having an average particle size of 20 μm or more) as the inorganic substance constituting the surface-modified inorganic substance. Surface-modified boron nitride) is preferably contained. A part or all of the inorganic nitride (preferably boron nitride) in the composition may constitute a surface-modified inorganic nitride (preferably surface-modified boron nitride) together with the surface modifier.
Further, the composition may contain a surface-modified inorganic oxide (preferably surface-modified aluminum) in which the inorganic substance constituting the surface-modified inorganic substance is an inorganic oxide (preferably aluminum oxide). A part or all of the inorganic oxide (preferably aluminum oxide) in the composition may constitute a surface-modified inorganic oxide (preferably surface-modified aluminum oxide) together with the surface modifier.
The surface-modifying inorganic substance can be formed, for example, by contacting the inorganic substance with the surface modifying agent. For example, an inorganic substance, a surface modifier, and other components constituting the composition of the present invention may be mixed to form a surface-modifying inorganic substance in the composition in the process of producing the composition of the present invention.
Further, for example, the inorganic substance and the surface modifying agent are mixed in a solvent to prepare a mixed solution containing the surface modifying inorganic substance, and the surface modifying inorganic substance is separated from the above mixed solution by means such as filtration and separation. The surface-modified inorganic substance may be obtained. The composition of the present invention may be prepared using the separated surface-modified inorganic substance.

As the surface modifier, a conventionally known surface modifier such as a carboxylic acid such as a long-chain alkyl fatty acid, an organic phosphonic acid, an organic phosphoric acid ester, and an organic silane molecule (silane coupling agent) can be used. In addition, for example, the surface modifiers described in JP-A-2009-502529, JP-A-2001-192500, and Japanese Patent No. 4694929 may be used.

The silane coupling agent is, for example, a compound having a hydrolyzable group directly bonded to a Si atom.
Examples of the hydrolyzable group include an alkoxy group (preferably 1 to 10 carbon atoms) and a halogen atom such as a chlorine atom.
The number of hydrolyzable groups directly bonded to the Si atom of the silane coupling agent is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more. There is no upper limit to the above number, for example, 10,000 or less.
It is also preferable that the silane coupling agent has a reactive group.
Specific examples of the reactive group include an epoxy group, an oxetanyl group, a vinyl group, a (meth) krill group, a styryl group, an amino group, an isocyanate group, a mercapto group, and an acid anhydride group.
The number of reactive groups contained in the silane coupling agent is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. There is no upper limit to the above number, for example, 10,000 or less.
Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltri. Examples thereof include methoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane, and 3-ureidopropyltriethoxysilane.

When the composition of the present invention contains a surface-modifying agent, a surface-modifying inorganic substance may be prepared in advance and used as a part of the raw material of the composition. That is, by mixing the surface-modified inorganic substance prepared in advance with various other components of the composition, all or part of the surface modifier and the inorganic substance can be obtained as a form contained in the surface-modified inorganic substance prepared in advance. It may be introduced into the composition.
Further, other than the surface modifier and the inorganic substance introduced in the form contained in the surface-modified inorganic substance, the surface modifier and / or the inorganic substance in a state where the surface-modified inorganic substance is not formed is mixed with other components of the composition. , All or part of the surface modifier and / or the inorganic material may be introduced into the composition. In this case, it is also preferable that the surface modifier is adsorbed on the surface of the inorganic substance in the mixing process to form the surface-modified inorganic substance in the composition. Further, in this case, a part of the surface modifying agent may be present in the composition in a state of not contributing to the formation of the surface modifying inorganic substance.

The surface modifier may be used alone or in combination of two or more.
When the composition contains a surface modifier, 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.
When the composition contains a surface modifier, 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 inorganic substances.
The mass ratio of the surface modifier to the inorganic substance (mass of the surface modifier adsorbed on the surface of the inorganic substance / mass of the inorganic substance) in the surface-modified inorganic substance is preferably 0.00001 to 0.5, preferably 0.0001 to 0.0001. 0.1 is more preferable.
When the composition contains a surface-modified inorganic substance, the content of the surface-modified inorganic substance is preferably 20% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, based on the total solid content of the composition. , 75% by mass or more is particularly preferable. The upper limit is less than 100% by mass, preferably 95% by mass or less, and more preferably 83% by mass or less.
When the composition contains a surface-modified nitride (preferably surface-modified boron nitride), the content of the surface-modified nitride (preferably surface-modified boron nitride) is 10 to 100% by mass with respect to the total surface-modified inorganic substance. Preferably, 40 to 100% by mass is more preferable, and 60 to 100% by mass is further preferable.

[Curing accelerator]
The composition also preferably contains a curing accelerator.
The curing accelerator preferably contains at least one selected from the group consisting of the compound represented by the general formula (P1) and the compound represented by the general formula (P2), and is represented by the general formula (P3). It is more preferable to contain the above compounds.
When the compound contained in the curing accelerator has an optical isomer, any optical isomer may be used. Further, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more. Similarly, in the general formulas (P1) to (P3) shown below, when an optical isomer is present, any optical isomer may be contained.

In the general formula (P1), L ^p represents a single bond or a divalent linking group.
Examples of the divalent linking group include an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S-), -SO _2- , and -NR. -(R is a hydrogen atom or an alkyl group), a divalent aliphatic hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group (-CH = CH-, etc.), an alkynylene group (-C≡C). -Etc.)), a divalent aromatic ring group (allylen group and a heteroarylene group), and a group combining these groups can be mentioned. The divalent linking group may further have a substituent. Examples of the substituent include the substituents exemplified in the above-mentioned Substituent Group Y.
The arylene group may be monocyclic or polycyclic, and preferably has 6 to 25 carbon atoms.
As the arylene group, a phenylene group, a naphthylene group, an anthrasenylene group or a binaphthylene group is preferable, and a binaphthylene group is more preferable.
As L ^p , a divalent aliphatic hydrocarbon group or a divalent aromatic ring group is preferable, and an alkylene group or an arylene group is more preferable.

R ^p11 to R ^p14 each independently represent a phenyl group which may have a substituent.
Examples of the substituent include the substituents exemplified in the above-mentioned substituent group Y, preferably an alkyl group, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

n _p represents 0 or 1. As n _p , 1 is preferable.

In the general formula (P2), R ^p21 to R ^p24 each independently represent a phenyl group which may have a substituent.
Examples of the substituent include the substituents exemplified in the above-mentioned substituent group Y, preferably an alkyl group, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

X ^- represents an anion.
Examples of the anion include hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, hexafluorophosphate ion, tetrafluoroborate ion, tetraphenylborate ion, dicyanamide ion, and alkylphosphate. Ions (eg, diethyl phosphate ion, etc.), hydrogen sulfate ion, dihydrogen phosphate ion, hydrogen phosphate ion, sulfamate ion, perchlorate ion, benzotriazolide anion, tetratolylborate anion (eg, eg) Tetra-p-tolylborate anion, etc.) can be mentioned.
As the anion, a tetratrilborate anion is preferable.

In the general formula (P3), R ^p31 to R ^p34 each independently represent a phenyl group which may have a substituent.
Examples of the substituent include the substituents exemplified in the above-mentioned substituent group Y, preferably an alkyl group, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

Examples of the curing accelerator include trisorthotrilphosfin, triphenylphosphine, trispalatrilphosfin, tri-t-butylphosphin, tri-i-butylphosphin, tricyclohexylphosfin, tri-2-furylphosfin, and dicyclohexylphenylphosphine. , Dit-butylphenylphosphine, 1,2-bis (diphenylphosphino) ethane, cis-1,2-bis (diphenylphosphino) ethylene, 1,3-bis (diphenylphosphino) propane, 1,4- Bis (diphenylphosphino) butane, 1,5-bis (diphenylphosfino) pentan, 4- (diphenylphosfino) styrene, 2- (diphenylphosfino) benzoic acid, 4- (diphenylphosfino) benzoic acid ,, 1,2-bis (diphenylphosphino) benzene, bis [2- (diphenylphosphino) phenyl] ether, 1,1'-bis (diphenylphosphino) ferrocene (dppf), BINAP (2,2'-bis (2,2'-bis) Diphenylphosphino) -1,1'-binaphthyl), TolBINAP (2,2'-bis [(4-methylphenyl) phosphino] -1,1'-binaphthyl), XylBINAP (2,2'-bis [(3) , 5-Dimethylphenyl) phosphino] -1,1'-binaphthyl), tBuBINAP (2,2'-bis (di-pt-butylphenylphosphino) -1,1'-binaphthyl), 2,2' -Bis [(4-t-butylphenyl) phosphino] -1,1'-binaphthyl, 2,2'-bis [(4-isopropylphenyl) phosphino] -1,1'-binaphthyl, 2,2'-bis [(Naphthalen-1-yl) phosphino] -1,1'-binaphthyl, 2,2'-bis [(naphthalen-2-yl) phosphino] -1,1'-binaphthyl, BICHEMP (2,2'-bis) (Dicyclohexylphosphino) -6,6'-dimethyl-1,1'-biphenyl), BPPFA (1- [1,2-bis- (diphenylphosphino) ferrosenyl] ethylamine), CHIRAPHOS (2,3-bis (2,3-bis) Diphenylphosphino) butane), CYCPHOS (1-cyclohexyl-1,2-bis (diphenylphosphino) ethan), DEFPHOS (1-substituted-3,4-bis (diphenylphosphino) pyrrolidine), DIOP (2,3) -Isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane) , SKEWPHOS (2,4-bis (diphenylphosphino) pentane), DuPHOS (substituted-1,2-bis (phosphorano) benzene), DIPAMP (1,2-bis [(o-methoxyphenyl) phenylphosphino] ethane) ), NORPHOS (5,6-bis (diphenylphosphino) -2-norbornene), PROPHOS (1,2-bis (diphenylphosphino) propane), PHANEPHOS (4,12-bis (diphenylphosphino)-[2 , 2'] -paracyclophane), substitution-2,2'-bis (diphenylphosphino) -1,1'-bipyridine, SEGPHOS ((4,4'-bis-1,3-benzodioxol)) -5,5'-Diyl-bis (diphenylphosphino)) and BIFAP (2,2'-bis (diphenylphosphanyl) -1,1'-bidibenzofuranyl) and other compounds containing phosphorus atoms Can be mentioned.

Examples of the curing accelerator include tetraphenylphosphonium tetraphenylborate (TPP-K), tetraphenylphosphonium tetra-p-tolylborate (TPP-MK), tetra-n-butylphosphonium laurate (TBP-LA), and bis ( Also onium salt-based curing accelerators such as tetra-n-butylphosphonium) pyromeritate and quaternary phosphonium compounds (phosphonium salts) such as bis (naphthalen-2,3-dioxy) phenylsilicate adducts of tetraphenylphosphonium. Can be mentioned.

Further, a boron trifluoride amine complex and a compound described in paragraph 0052 of JP2012-06722A can also be mentioned.
In addition, 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name). 1.2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl -2-Methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2- Undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2PZCNS-PW), 2,4-diamino-6- [2'-methylimidazolyl- (1'')]-Ethyl-s-triazine (trade name; 2MZ-A), 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine (trade name; C11Z) -A), 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine (trade name; 2E4MZ-A), 2,4-diamino- 6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-) PW), 2-phenyl-4-methyl-5-hydroxymethylimidazole (trade name; 2P4MHZ-PW), 1-cyanoethyl-2-phenylimidazole (trade name; 2PZ-CN), 2,4-diamino-6- [2'-Methylimidazolyl- (1')]-ethyl-s-triazine (trade name; 2MZA-PW) and 2,4-diamino-6- [2'-methylimidazolyl- (1')]- Examples thereof include imidazole-based curing accelerators such as ethyl-s-triazine isocyanuric acid adduct (trade name; 2MAOK-PW) (all manufactured by Shikoku Kasei Kogyo Co., Ltd.). Further, as a triarylphosphine-based curing accelerator, the compound described in paragraph 0052 of JP-A-2004-043405 can also be mentioned. Examples of the phosphorus-based curing accelerator to which triphenylborane is added to triarylphosphine include the compounds described in paragraph 0024 of JP-A-2014-005382.

The molecular weight of the curing accelerator is often 200 or more, preferably 250 or more, more preferably 400 or more, further preferably 430 or more, and particularly preferably 600 or more. The upper limit is preferably 10,000 or less, more preferably 1000 or less, and even more preferably 800 or less.
When the molecular weight of the curing accelerator is 250 or more, when heat treatment (for example, evaluation of solder heat resistance II in the column of Examples) is performed at a high temperature, the curing accelerator itself and / or the curing accelerator The volatilization of pyrolyzed products can be further suppressed, and the solder heat resistance is more excellent. Further, when the molecular weight of the curing accelerator is 10,000 or less, it easily functions as a curing accelerator.

Among them, the curing accelerator preferably contains a compound containing a phosphorus atom, and preferably contains a phosphonium salt, because the effect of the present invention is more excellent. The curing accelerator may be a compound containing a phosphorus atom or a phosphonium salt itself. When a phosphonium salt is used as a curing accelerator, the storage stability of the semi-cured film formed from the composition is also improved.
The content of the compound containing a phosphorus atom or the phosphonium salt is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 80 to 100% by mass, based on the total mass of the curing accelerator.

The curing accelerator may be used alone or in combination of two or more.
The content of the curing accelerator is preferably 0.002% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.07% by mass or more, based on the total solid content of the composition. The content of the curing accelerator is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, based on the total solid content of the composition.
The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.55% by mass or more, based on the total epoxy compound. The content of the curing accelerator is preferably 40% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total epoxy compound.

[Ion scavenger]
The composition of the present invention may contain an ion scavenger.
The ionic scavenger adsorbs ionic impurities in the composition or in the heat conductive material formed with the composition. Thereby, even when the heat conductive material absorbs moisture in the composition, the insulating property of the heat conductive material can be better maintained.
Examples of the ion scavenger include an inorganic ion scavenger as described above and an organic ion scavenger.
Examples of the organic ion scavenger include triazinethiol compounds; triazineamine compounds; benzoimidazole compounds; benzotriazole compounds; aminotriazole compounds; and bisphenol-based reducing agents.
In addition, all or a part of the above-mentioned inorganic substances may also function as an ion scavenger.

Examples of the triazine thiol compound include 2-dibutylamino-4,6-dimercapto-s-triazine.
Examples of the benzimidazole compound include benzimidazole.
Examples of the benzotriazole compound include 1H-benzotriazole, carboxybenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl). Benzotriazole and 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4-tert-octylphenol] can be mentioned.
Examples of the aminotriazole compound include 3-amino-1,2,4-triazole and 3,5-diamino-1,2,4-triazole.
Examples of the bisphenol-based reducing agent include 2,2'-methylenebis- (4-ethyl-6-t-butylphenol) and 4,4'-butylidenebis- (6-t-butyl-3-methylphenol). Can be mentioned.

Commercially available products may be used as the ion scavenger, for example, DHF-4A, DHT-4A, DHT-4A-2, DHT-4C, Kyoward 500, KW-2000, and KW-2100 (trade name, Kyowa). IXE-100, IXE-500, IXE-600, IXE-700F, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS-A2, and IXEPLAS-B1 (trade name, manufactured by Toagosei Co., Ltd.) ); Gisnet DB (trade name, manufactured by Sankyo Pharmaceutical Co., Ltd.); VD-3 and VD-5 (trade name, manufactured by Shikoku Kasei Co., Ltd.); and Yoshinox BB (trade name, manufactured by Yoshitomi Pharmaceutical Co., Ltd.). ..

When the composition contains an ion scavenger, the content of the ion scavenger (inorganic ion scavenger and / or organic ion scavenger) is 0.01 to 10 with respect to the total solid content of the composition. The mass% is preferable, 0.1 to 20% by mass is more preferable, and 0.2 to 10% by mass is further preferable.
When the ion scavenger contains an inorganic ion scavenger, a part or all of the ion scavenger may be an inorganic substance at the same time.
The ion scavenger may be used alone or in combination of two or more.

〔solvent〕
The composition may further contain a solvent.
The type of solvent is not particularly limited, and it is preferably an organic solvent. Examples of the organic solvent include cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane, tetrahydrofuran and the like.
When the composition contains a solvent, the content of the solvent is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 50 to 80% by mass. Is more preferable.
The content of the solvent is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, still more preferably 20 to 50% by mass, based on the total mass of the composition.

[Method for producing composition]
The method for producing the composition is not particularly limited, and a known method can be adopted. For example, the above-mentioned various components can be mixed and produced. When mixing, various components may be mixed all at once or sequentially.
The method of mixing the components is not particularly limited, and a known method can be used. The mixing device used for mixing is preferably a liquid disperser, for example, a stirrer such as a rotating revolution mixer, a high-speed rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure injection disperser, an ultrasonic disperser, a bead mill, etc. And a homogenizer can be mentioned. The mixing device may be used alone or in combination of two or more. Degassing may be performed before, after, and / or at the same time as mixing.

[Curing method of composition]
The composition of the present invention is preferably a composition for forming a heat conductive material.
The composition of the present invention is cured to obtain a heat conductive material.
The curing method of the composition is not particularly limited, but a thermosetting reaction is preferable.
The heating temperature during the thermosetting reaction is not particularly limited. For example, it may be appropriately selected in the range of 50 to 250 ° C. Further, when the thermosetting reaction is carried out, heat treatments having different temperatures may be carried out a plurality of times.
The curing treatment is preferably performed on a film-like or sheet-like composition. Specifically, for example, the composition may be applied to form a film and a curing reaction may be carried out.
When performing the curing treatment, it is preferable to apply the composition on the substrate to form a coating film and then cure. At this time, a different base material may be brought into contact with the coating film formed on the base material, and then the curing treatment may be performed. The cured product (heat conductive material) obtained after curing may or may not be separated from one or both of the substrates.
Further, when performing the curing treatment, the composition may be applied on different substrates to form coating films, and the curing treatment may be performed in a state where the obtained coating films are in contact with each other. The cured product (heat conductive material) obtained after curing may or may not be separated from one or both of the substrates.

The curing treatment may be completed when the composition is in a semi-cured state. Further, after the composition is made into a semi-cured state, further curing treatment may be carried out to complete the curing.
The curing treatment for making the composition semi-cured (also referred to as "semi-cured treatment") and the curing treatment for completing the curing (also referred to as "main curing treatment") are divided into separate steps. You may go.

For example, in the semi-curing treatment, a composition is applied onto a substrate to form a coating film, and then the coating film on the substrate is heated without pressure to form a semi-cured heat conductive material (“semi-cured”). It may be a "cured film" or a "semi-cured sheet"), or the coating film on the substrate may be heated or the like to form a semi-cured film while being pressed together. In the case of press working, the press working may be carried out before or after the above heating or the like, or may be carried out during the press working. When press working is performed in the semi-cured film, it may be easy to adjust the film thickness of the obtained semi-cured film and / or 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 different substrates are laminated, or the semi-curing treatment may be performed without laminating the coating films. The semi-curing treatment may be carried out in a state where the coating film formed from the composition is further in contact with a material other than the coating film.

The obtained semi-cured film may be used as it is as a heat conductive material, or may be used as a completely cured heat conductive material after the semi-cured film is further subjected to the main curing treatment.
In the main curing treatment, the semi-cured film may be heated as it is without pressure, or may be heated after being pressed or while being pressed. At this time, in the main curing treatment, the main curing treatment may be performed in a state where the separate semi-cured films are laminated, or the main curing treatment may be performed without laminating the semi-cured films.
Further, the main curing treatment may be carried out in a state where the semi-cured film is arranged so as to be in contact with the device or the like to be used. It is also preferable that the device and the heat conductive material of the present invention are adhered to each other by this curing treatment.

There are no restrictions on the press used for the press working that may be performed during the semi-curing treatment and / or the curing treatment in the main curing treatment, and for example, a flat plate press may be used or a roll press may be used. good.
When a roll press is used, for example, a substrate with a coating film obtained by forming a coating film on the substrate is sandwiched between a pair of rolls in which two rolls face each other, and the above pair of rolls is used. It is preferable to apply pressure in the film thickness direction of the coated substrate while rotating the substrate to pass the coated substrate. In the above-mentioned base material with a coating film, the base material may be present on only one side of the coating film, or the base material may be present on both sides of the coating film. The substrate with a coating film may be passed through the roll press only once or may be passed a plurality of times.
In the semi-curing treatment and / or the curing treatment in the main curing treatment or the like, only one of the treatment by the flat plate press and the treatment by the roll press may be carried out, or both may be carried out.

For the production of heat conductive materials including curing reaction, refer to "High heat conductive composite material" (CMC Publishing, by Yutaka Takezawa).

The shape of the heat conductive material is not particularly limited, and can be molded into various shapes depending on the application. A typical shape of the molded heat conductive material is, for example, a sheet shape.
That is, the heat conductive material obtained by using the composition of the present invention is preferably a heat conductive sheet.
Further, the thermal conductivity of the heat conductive material obtained by using the composition of the present invention is preferably isotropic rather than anisotropic.

It is also preferable that the heat conductive material (preferably a heat conductive sheet) has suppressed hygroscopicity.
Specifically, the heat conductive material (preferably a heat conductive sheet) preferably has a mass change rate of less than 1.0%, more preferably less than 0.7%, as determined by the following formula. It is more preferably less than 0.5%. The lower limit of the mass change rate is usually 0% by mass or more.
W1: Mass of the heat-conducting material (preferably a heat-conducting sheet) in a dry state after being dried in an environment of 120 ° C. for 2 hours W2: The heat-conducting material (preferably a heat-conducting sheet) in a dry state is 85 ° C. The mass of the heat-conducting material (preferably a heat-conducting sheet) in a moisture-absorbing state after being left in an environment of 85 RH% for 24 hours. Drying in an environment of 120 ° C. when determining W1 was sufficiently dehumidified. It will be done in the environment.

The heat conductive material is preferably insulating (electrically insulating). In other words, the composition of the present invention is preferably a thermally conductive insulating composition.
For example, the volume resistivity of the heat conductive material at 23 ° C. and 65% relative humidity is preferably 10 ¹⁰ Ω · cm or more, more preferably 10 ¹² Ω · cm or more, and even more preferably 10 ¹⁴ Ω · cm or more. The upper limit is not particularly limited, but is usually 10 ¹⁸ Ω · cm or less.

[Use of heat conductive materials]
The heat conductive material obtained by using the composition of the present invention can be used as a heat radiating material such as a heat radiating sheet, and can be used for heat radiating applications of various devices. More specifically, a device with a heat conductive layer can be produced by arranging a heat conductive layer containing the heat conductive material of the present invention on the device, and heat generated from the device can be efficiently dissipated by the heat conductive layer. The heat conductive layer may be a heat conductive layer including a heat conductive multilayer sheet described later.
Since the heat conductive material obtained by using the composition of the present invention has sufficient heat conductivity and high heat resistance, it is used for various electric devices such as personal computers, general household appliances, and automobiles. Suitable for heat dissipation of power semiconductor devices.
Further, since the heat conductive material obtained by using the composition of the present invention has sufficient heat conductivity even in a semi-cured state, it reaches light for photocuring such as gaps between members of various devices. It can also be used as a heat radiating material to be placed in areas where it is difficult to make it. In addition, since it has excellent adhesiveness, it can also be used as an adhesive having thermal conductivity.

The heat conductive material obtained by using the composition of the present invention may be used in combination with other members other than the members formed from the present composition.
For example, the heat conductive material (heat conductive sheet or the like) may be combined with a support (adhesion material) other than the layer formed from the present composition.
Examples of the support (adhesive material) include a plastic material, a metal material, and glass. Examples of the plastic material include polyester such as polyethylene terephthalate (PET), polycarbonate, acrylic resin, epoxy resin, polyurethane, polyamide, polyolefin, cellulose derivative, and silicone. Examples of the metal material include copper and aluminum.
The support (adhesive material) is also preferably in the form of a sheet.
The film thickness of the sheet-shaped heat conductive material (heat conductive sheet) is preferably 100 to 300 μm, more preferably 150 to 250 μm.

Further, an adhesive layer and / or an adhesive layer may be combined with the heat conductive material (preferably a heat conductive sheet).
By bonding the heat conductive material to an object such as a device to which heat should be transferred through such an adhesive layer and / or an adhesive layer, a stronger bond between the heat conductive material and the object is performed. Can be realized. The heat conductive material formed from the composition of the present invention has good adhesion to the adhesive layer and the pressure-sensitive adhesive layer, and can suppress peeling at the interface between the heat conductive material and the adhesive layer or the pressure-sensitive adhesive layer.
For example, as the heat conductive multilayer sheet, a heat conductive multilayer sheet having a heat conductive sheet and an adhesive layer or an adhesive layer provided on one side or both sides of the heat conductive sheet may be produced. ..
In addition, one of the adhesive layer and the pressure-sensitive adhesive layer may be provided on one side or both sides of the heat conductive sheet, respectively, or both may be provided. An adhesive layer may be provided on one surface of the heat conductive sheet, and an adhesive layer may be provided on the other surface. Further, the adhesive layer and / or the adhesive layer may be partially provided on one side or both sides of the heat conductive sheet, or may be provided on the entire surface.
As described above, in the present invention, the heat conductive material such as the heat conductive sheet may be in a semi-cured state (semi-cured film), and the heat conductive sheet in the heat conductive multilayer sheet may be in a semi-cured state. .. The adhesive layer in the heat conductive multilayer sheet may be in a cured state, a semi-cured state, or an uncured state.

The present invention will be described in more detail below based on examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention should not be construed as limiting by the examples shown below.

<< Test X >>
First, Test X (Examples 1 to 75, Comparative Examples 1 and 2) was carried out based on the conditions and procedures as shown below.

[Preparation and evaluation of composition]
[Various ingredients]
The various components used in Examples and Comparative Examples are shown below.
In addition, the components to be used in the test Y described later are also shown below.

<Phenol compound>
The phenolic compounds used in Examples and Comparative Examples are shown below.

-A-3: MEH-7500 (Phenolic compound manufactured by Meiwa Kasei, which does not have a triazine skeleton)

<Epoxy compound>
The epoxy compounds used in Examples and Comparative Examples are shown below.
The weight average molecular weight of B-8 is 3000, and the average value of n values of B-9 is 10.

<Maleimide compound>
The maleimide compounds used in Examples and Comparative Examples are shown below.

<Cyanate compound>
The cyanate compounds used in Examples and Comparative Examples are shown below.
-G-1: TA (manufactured by Mitsubishi Gas Chemical Company, 2,2'-di (4-cyanatophenyl) propane)
G-2: TA-100 (pre-polymerized product of 2,2'-di (4-cyanatophenyl) propane manufactured by Mitsubishi Gas Chemical Company, Inc.)
-G-3: AROCY XU371 (manufactured by HUNSMAN, phenol novolac cyanate)
・ G-4: P-201 (manufactured by Mitsubishi Gas Chemical Company)

<Inorganic nitride, inorganic oxide, or its surface modifier>
The following shows the inorganic nitrides, inorganic oxides, or surface-modified products thereof (surface-modified inorganic nitrides or surface-modified inorganic oxides) used in Examples and Comparative Examples. In any of the surface-modified products (surface-modified inorganic nitride or surface-modified inorganic oxide), the content of the surface-modifying agent with respect to the total mass of the surface-modified product was more than 0% by mass and less than 1% by mass. ..
-HP-40: Aggregate boron nitride, average particle size: 40 μm, manufactured by Mizushima Alloy Iron Co., Ltd.-AA-3: Aluminum oxide, average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd.-PTX-60: Aggregate boron nitride, average Particle size: 60 μm, Momentive, SP-3: scaly boron nitride, average particle size: 4 μm, Denka, BN1: Surface-modified boron nitride produced by the production method 1 shown below, BN2: shown below. Surface-modified Boron Nitride / BN3 manufactured by Production Method 2: Surface-Modified Boron Nitride / BN4 manufactured by Production Method 3 shown below: Surface-Modified Boron Nitride / BN5 manufactured by Production Method 4 shown below: Surface-modified Boron Nitride / BN6 manufactured by the manufacturing method 5 shown below: Surface-modified boron nitride manufactured by the manufacturing method 6 shown below / BN7: Surface-modified boron nitride manufactured by the manufacturing method 7 shown below / BN8: The following Surface-modified boron nitride produced by the production method 8 shown in BN9: Surface-modified boron nitride produced by the production method 9 shown below BN10: Surface-modified boron nitride produced by the production method 10 shown below.

(Manufacturing method 1 (Manufacturing of BN1))
Boron nitride (PTX-60) (50 g) was added to NaOH water (NaOH: 40 g / water: 400 ml) and stirred. After further adding sodium persulfate water (sodium persulfate: 9.6 g / water: 100 ml) to the NaOH water, the temperature of the NaOH water was raised to 50 ° C., and the mixture was further stirred for 3 hours (modification step). A three-one motor manufactured by Shinto Kagaku Co., Ltd. was used for stirring, and the stirring was performed at 150 rpm.
After cooling the NaOH water to room temperature, the boron nitride in the NaOH water is collected by filtration, and the collected boron nitride is washed with water (500 ml) and acetonitrile (250 ml) to obtain modified boron nitride 1. Obtained.
The obtained modified boron nitride 1 was stirred in acetonitrile (100 ml), and a hydrolysis adjusting solution (1.25 g) of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: X12-984S) was further added to the acetonitrile. .. The acetonitrile was stirred at room temperature for 3 hours to perform an adsorption treatment (adsorption step).
After the modified boron nitride 1 in acetonitrile is collected by filtration, the removed modified boron nitride 1 is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 1 (“BN1”). Also called).
The hydrolysis adjustment solution for the silane coupling agent is a mixture of silane coupling agent (1 g), ethanol (500 μl), 2-propanol (500 μl), water (720 μl), and acetic acid (100 μl), and the mixture is stirred for 1 hour. Adjusted by doing. In the subsequent production methods, the formulation of the hydrolysis adjusting solution of the silane coupling agent is the same unless otherwise specified.
Further, "X12-984S" is a polymer type silane coupling agent having an epoxy group and an ethoxysilyl group.
In the production method 1, a liquid (aqueous solution) in which NaOH water (NaOH: 40 g / water: 400 ml), boron nitride 50 g, and sodium persulfate water (sodium persulfate: 9.6 g / water: 100 ml) are mixed. The pH of was 14.

(Manufacturing method 2 (Manufacturing of BN2))
Boron nitride (PTX-60 described above) (50 g) was added to water (400 ml) and stirred to obtain a mixed solution. After further adding 30% by mass hydrogen peroxide solution (30 ml) to the mixed solution, the temperature of the mixed solution was raised to 50 ° C., and the mixture was further stirred for 3 hours. A three-one motor manufactured by Shinto Kagaku Co., Ltd. was used for stirring, and the stirring was performed at 150 rpm.
After cooling the mixed solution to room temperature, the boron nitride in the mixed solution is collected by filtration, and the collected boron nitride is washed with water (500 ml) and acetonitrile (250 ml) to obtain modified boron nitride. rice field.
The obtained modified boron nitride was stirred in acetonitrile (100 ml), and a hydrolysis adjusting solution (1.25 g) of a silane coupling agent (KBM-403) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment.
After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 2 (also referred to as "BN2"). I got).
In addition, "KBM-403" is 3-glycidoxypropyltrimethoxysilane.
In the production method 2, the pH of the liquid (aqueous solution) in which water (400 ml), 50 g of boron nitride, and 30 mass% hydrogen peroxide solution (30 ml) was mixed was 5.

(Manufacturing method 3 (Manufacturing of BN3))
Surface-modified boron nitride 3 (also referred to as "BN3") was obtained by the same production method as in Production Method 1 except that the NaOH water in Production Method 1 was changed to (NaOH: 0.02 g / water: 400 ml).
In the production method 3, a liquid (NaOH: 0.02 g / water: 400 ml) mixed with NaOH water (NaOH: 0.02 g / water: 400 ml), 50 g of boron nitride, and sodium persulfate water (sodium persulfate: 9.6 g / water: 100 ml) ( The pH of the aqueous solution) was 11.

(Manufacturing method 4 (Manufacturing of BN4))
Boron nitride (PTX-60 described above) (50 g) was heated at 1000 ° C. for 1 hour in an oxidizing atmosphere to obtain modified boron nitride.
The obtained modified boron nitride was stirred in acetonitrile (100 ml), and a hydrolysis adjusting solution (1.25 g) of a silane coupling agent (KBM-403) was further added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment.
After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 4 (also referred to as "BN4"). I got).

(Manufacturing method 5 (Manufacturing of BN5))
Boron nitride (PTX-60, described above) (50 g) was stirred in acetonitrile (100 ml), and a hydrolysis adjusting solution (1.25 g) of a silane coupling agent (KBM-403) was further added to the acetonitrile. .. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment.
After the boron nitride in acetonitrile is collected by filtration, the collected boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 5 (also referred to as “BN5”). Got

(Manufacturing method 6 (Manufacturing of BN6))
Boron nitride (HP-40 above) (15 g) was subjected to vacuum plasma treatment (gas type: O ₂ , pressure: 30 Pa, output: 500 W) using Plascleaner PDC210 (manufactured by Yamato Scientific Co., Ltd.). Boron nitride to be treated was stirred every 5 minutes of vacuum plasma treatment, and vacuum plasma treatment was performed until the total treatment time reached 30 minutes to obtain modified boron nitride particles.
The obtained modified boron nitride was stirred in acetonitrile (30 ml), and a hydrolysis adjusting solution (0.42 g) of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: X12-984S) was further added to the acetonitrile. .. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment.
After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (30 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 6 (also referred to as "BN6"). ) Was obtained.
Further, "X12-984S" is a polymer type silane coupling agent having an epoxy group and an ethoxysilyl group.

(Manufacturing method 7 (Manufacturing of BN7))
Boron nitride (HP-40, 50 g described above) 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 temperature of the NaOH aqueous solution was raised to 50 ° C., and the mixture was further stirred for 3 hours. Stirring was performed using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) at a rotation speed of 150 rpm. After cooling the aqueous NaOH solution to room temperature, the boron nitride in the aqueous NaOH solution is collected by filtration, and the collected boron nitride is washed with water (500 ml) and acetonitrile (250 ml) to obtain modified boron nitride. Obtained.
The obtained modified boron nitride was stirred in acetonitrile (100 ml), and a hydrolysis adjusting solution (1.25 g) of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: X12-984S) was further added to the acetonitrile. .. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment. After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 7 (also referred to as "BN7"). ) Was obtained.

(Manufacturing method 8 (Manufacturing of BN8))
Boron nitride (HP-40, 50 g described above) was added to water (400 ml) and stirred to obtain a mixed solution. Sodium hypochlorite water (sodium hypochlorite pentahydrate: 48 g / water: 100 ml) was further added to the mixed solution, the temperature of the mixed solution was raised to 50 ° C., and the mixture was further stirred for 3 hours. A three-one motor manufactured by Shinto Kagaku Co., Ltd. was used for stirring, and the stirring was performed at 150 rpm.
After cooling the mixed solution to room temperature, the boron nitride in the mixed solution is collected by filtration, and the collected boron nitride is washed with water (500 ml) and acetonitrile (250 ml) to obtain modified boron nitride. rice field.
The obtained modified boron nitride was stirred in acetonitrile (100 ml), and a hydrolysis adjusting solution (1.25 g) of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: X12-984S) was further added to the acetonitrile. .. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment. After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 8 (also referred to as "BN8"). I got).

(Manufacturing method 9 (Manufacturing of BN9))
Boron nitride (HP-40, 50 g described above) was heated at 1000 ° C. for 1 hour to obtain modified boron nitride. The obtained modified boron nitride was washed with water (500 ml), filtered, and then stirred in acetonitrile (100 ml). Further, a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) was added to the acetonitrile. A hydrolysis control solution (1.25 g) was added. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment. After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 9 (also referred to as "BN9"). I got).
In addition, "KBM-403" is 3-glycidoxypropyltrimethoxysilane.

(Manufacturing method 10 (Manufacturing of BN10))
Boron nitride (HP-40, 50 g described above) was heated at 900 ° C. for 4 hours to obtain modified boron nitride. The obtained modified boron nitride was washed with water (500 ml), filtered, and then stirred in acetonitrile (100 ml). Further, a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) was added to the acetonitrile. A hydrolysis control solution (1.25 g) was added. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment. After the modified boron nitride in acetonitrile is collected by filtration, the removed modified boron nitride is washed with acetonitrile (100 ml) and dried in an oven at 40 ° C. to obtain surface-modified boron nitride 10 (also referred to as "BN10"). I got).

<Curing accelerator>
The curing accelerators used in Examples and Comparative Examples are shown below.
The values shown in parentheses after each compound name indicate the molecular weight of each compound.
C-1: Tris orthotrilphosphine (304.37)
C-2: Triphenylphosphine (262.29)
C-3: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) (204.23)
C-4: TPP-MK (Tetraphenylphosphonium Tetra-p-Trillbolate) (658.62)
C-5: (S)-(-)-BINAP ((S)-(-)-2,2'-bis (diphenylphosphino) -1,1'-binaphthyl) (622.69)
C-6: (S)-(-)-TolbINAP ((S)-(-)-2,2'-bis (di-p-tolylphosphino) -1,1'-binaphthyl) (678.80)
C-7: (S)-(-)-XylBINAP ((S)-(-)-2,2'-bis [di (3,5-kisilyl) phosphino] -1,1'-binaphthyl) (734) .90)
C-8: (R)-(+)-BINAP ((R)-(+) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl) (622.69)
C-9: (R)-(+)-TolbINAP ((R)-(+) -2,2'-bis (di-p-tolylphosphino) -1,1'-binaphthyl) (678.80)
C-10: (R)-(+)-XylBINAP ((R)-(+) -2,2'-bis [di (3,5-kisilyl) phosphino] -1,1'-binaphthyl) (734) .90)
C-11: (±) -BINAP ((±) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl) (622.69)

<Ion scavenger>
The ion scavengers used in Examples and Comparative Examples are shown below.
・ F-1: KW-2000, aluminum oxide / magnesium oxide solid solution (Mg _0.7 Al _0.3 O _1.15 ), manufactured by Kyowa Chemical Industry Co., Ltd. ・ F-2: KW-2100, aluminum oxide / magnesium oxide solid solution , Kyowa Kagaku Kogyo Co., Ltd. ・ F-3: KW-2200, Aluminum oxide / magnesium oxide solid solution, Kyowa Kagaku Kogyo Co., Ltd. ・ F-4: IXE-600, Bi, Sb system, Toa Synthetic Co., Ltd. ・ F-5: IXE-700F, Mg, Al series, manufactured by Toa Synthetic Co., Ltd. ・ F-6: IXE-6107, Zr, Bi series, manufactured by Toa Synthetic Co., Ltd.

<Solvent>
Cyclopentanone was used as the solvent.

[Preparation of composition]
After mixing the solvent, phenol compound, epoxy compound used as desired, ion scavenger used as desired, specific compound (maleimide compound and / or cyanate compound), and curing accelerator in this order, an inorganic substance or Surface-modified inorganic substances were added. The obtained mixture was treated with a rotation revolution mixer (manufactured by THINKY, Awatori Rentaro ARE-310) for 5 minutes to obtain a composition (curable composition) of each Example or Comparative Example.

Here, the amount of the solvent added was set so that the solid content concentration of the composition was 50 to 80% by mass.
The solid content concentration of the composition was adjusted for each composition within the above range so that the viscosities of the compositions were about the same.
When the composition contains both the phenol compound and the epoxy compound, the total content of the epoxy compound and the phenol compound is shown in the "total amount (% by mass)" column in Table 1 with respect to the total solid content of the composition. The addition amount was adjusted so that the amount was equal to that of the epoxy compound and the phenol compound (the number of epoxy groups in the epoxy compound was equal to the number of hydroxyl groups in the phenol compound).
When the composition contains only one of the phenol compound and the epoxy compound, the content of one of the components is the amount shown in the "total amount (% by mass)" column in Table 1 with respect to the total solid content of the composition. The amount of addition was adjusted so as to be.
In the composition, the amounts of the curing accelerator, the inorganic substance (inorganic nitride, inorganic oxide, or its surface modifier), the ion scavenger, the maleimide compound, and the cyanate compound are respectively added to the total solid content of the composition. On the other hand, the amount (% by mass) shown in parentheses in each cell in Table 1 was set.

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

[Making a heat conductive sheet]
The surface of the obtained semi-cured sheet opposite to the PET film was covered with a release-treated PET film and heat-pressed under air (hot plate temperature 180 ° C., pressure 20 MPa for 5 minutes). Then, it was heat-treated at 180 ° C. for 90 minutes under normal pressure to obtain a resin sheet. The PET films on both sides of the resin sheet were peeled off to obtain a heat conductive sheet (heat conductive material) having an average film thickness of 120 μm.

[Evaluation method of thermal conductivity]
(1) Using "LFA467" manufactured by NETZSCH, the thermal diffusivity in the thickness direction of the heat conductive sheet was measured by a laser flash method.
(2) The specific gravity of the heat conductive sheet was measured by the Archimedes method (using the "solid specific gravity measurement kit") using the balance "XS204" manufactured by Metler Toledo.
(3) Using "DSC320 / 6200" manufactured by Seiko Instruments Inc., the specific heat of the heat conductive sheet at 25 ° C. was determined under the heating condition of 10 ° C./min.
(4) The obtained thermal diffusivity was multiplied by the specific gravity and the specific heat to calculate the thermal conductivity of the heat conductive sheet.

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

[Evaluation of Tg (heat resistance)]
The Tg of the obtained heat conductive sheet was measured.
For the measurement, a dynamic viscoelasticity measuring device "Rheogel-E4000" manufactured by UBM was used, and the tanδ peak at a frequency of 1 Hz was defined as Tg. The temperature rising rate was 5 ° C./min, and the measurement was carried out in the range of 25 to 300 ° C.

The Tg of the heat conductive sheet was classified according to the following criteria, and the heat resistance of the heat conductive sheet (heat conductive material) obtained by using the composition of each Example or Comparative Example was evaluated.
A +: 180 ° C or higher A: 170 ° C or higher and lower than 180 ° C B: 160 ° C or higher and lower than 170 ° C C: 150 ° C or higher and lower than 160 ° C D: Less than 150 ° C

[Evaluation of insulation]
A voltage of 1 kV was applied to the sample (a heat conductive sheet having a film thickness of 120 μm produced by the above method) in an environment of 85 ° C. and 85% RH, and the time until the sample was dielectrically broken down was measured.
The time until the sample was dielectrically broken down was classified according to the following criteria, and the heat insulating property of the heat conductive sheet (heat conductive material) obtained by using the composition of each Example or Comparative Example was evaluated.
A: 500 hours or more B: 100 hours or more and less than 500 hours C: 50 hours or more and less than 100 hours D: less than 50 hours

[Evaluation of hygroscopicity]
The hygroscopicity of the obtained heat conductive sheet was evaluated.
The heat conductive sheet was dried at 120 ° C. for 2 hours using a sufficiently dehumidified dryer to obtain a dried heat conductive sheet. The heat conductive sheet in a dry state was placed in an environment of 85 ° C. and 85 RH% for 24 hours to obtain a heat conductive sheet in a hygroscopic state.
The mass of these heat conductive sheets was compared with the following formula to determine the mass change rate, and the hygroscopicity of the heat conductive sheets was evaluated in light of the following categories. The smaller the mass change rate, the more the hygroscopicity is suppressed, which is preferable.
Mass change rate (%) = (W2-W1) / W1 × 100
W1: Mass of the heat conductive sheet in a dry state after being dried in an environment of 120 ° C. for 2 hours W2: Moisture absorption state after the heat conductive sheet in a dry state is placed in an environment of 85 ° C. and 85 RH% for 24 hours. Mass of heat conductive sheet A: Mass change rate is less than 0.5% B: Mass change rate is 0.5% or more and less than 0.7% C: Mass change rate is 0.7% or more and less than 1.0% D : Mass change rate is 1.0% or more

[Evaluation of solder heat resistance]
After peeling the PET film from the obtained semi-cured sheet, it is sandwiched between a copper substrate with a thickness of 2 mm and a copper foil with a thickness of 0.15 mm, and heat pressed under air (treatment at a hot plate temperature of 180 ° C. and a pressure of 20 MPa for 5 minutes). Then, a laminated body having a structure of "copper substrate-heat conductive sheet-copper foil" was obtained.
The 0.15 mm copper foil in the laminate is etched into a circular shape with a diameter of 2 cm, and the laminate has a solder heat resistance having the structure of "copper substrate-heat conductive sheet-circular copper foil with a diameter of 2 cm". It was used as a test sample.
The above sample was heated at 300 ° C. for 3 minutes and then cooled to room temperature (25 ° C.) at least once. Then, a circular copper foil having a diameter of 2 cm was peeled off from the sample that had been heat-treated one or more times.
Visually observe the fracture state of the peeled sample, and if the heat conductive sheet is aggregated and broken on the entire peeled surface, pass the test, and pass between "copper substrate-heat conductive sheet" and / or "heat conductive sheet-". If interfacial peeling occurred in a part or the entire surface between the "circular copper foils with a diameter of 2 cm", it was rejected.
Based on the relationship between pass and fail with respect to the number of heat treatments, the solder heat resistance of the heat conductive sheet was evaluated in light of the following categories.
A: Passed even after 3 heat treatments B: Passed even after 2 heat treatments, but failed after 3 heat treatments C: Passed even after 1 heat treatment However, it failed when it was performed twice. D: It failed when the heat treatment was performed once.

[Evaluation of solder heat resistance II]
In the above [evaluation of solder heat resistance], the solder heat resistance II was evaluated by the same procedure except that the heating temperature was changed from 300 ° C to 320 ° C.

[result]
Table 1 is shown below.
Table 1 shows the composition of the solid content and the test results of the composition in each Example or Comparative Example.

From the results shown in the table, it was confirmed that the effect of the present invention can be realized by using the composition of the present invention.

Among them, it was confirmed that the effect of the present invention is more excellent when the inorganic substance contains substantially only boron nitride and an inorganic ion scavenger (see comparison of results of Examples 5, 21 and 22).

It was confirmed that the effect of the present invention was more excellent when the composition contained surface-modified boron nitride (see comparison of results of Examples 5, 24-28, 54-58, etc.).

It was confirmed that the effect of the present invention is more excellent when the curing accelerator contains a compound containing a phosphorus atom or a phosphonium salt (see comparison of results of Examples 2 to 5 and the like).
Further, it was confirmed that the effect of the present invention is more excellent when the curing accelerator contains a compound represented by the general formula (P3) (see Example 3, Comparison of Results of 59 to 65).

It was confirmed that the effect of the present invention is more excellent when the maleimide compound has two maleimide groups (see comparison of the results of Examples 3 and 51, etc.).
When the maleimide compound is a compound represented by the general formula (1) in which m is 1, n is 1, and L ¹ is a divalent linking group having 3 to 15 carbon atoms, the present invention is used. It was confirmed that the effect was superior (see comparison of the results of Examples 5 to 9 and the like).

The phenol compound has a triazine skeleton, and the total content of the phenol compound having a triazine skeleton and the epoxy compound having a triazine skeleton is 5 to 80 mass with respect to the total content of the total phenol compound and the total epoxy compound. When it is%, it was confirmed that the effect of the present invention is more excellent (see comparison of results of Examples 5, 10 to 20 and the like).

It was confirmed that the effect of the present invention was more excellent when the content of the inorganic substance in the total solid content of the composition was 83% by mass or less (see comparison of the results of Examples 24 and 30).

It was confirmed that the effect of the present invention was more excellent when the content of the maleimide compound was 100% by mass or less with respect to the total content of the epoxy compound and the phenol compound (results of Examples 24 and 29). See comparison etc.).

It was confirmed that the effect of the present invention was more excellent when the composition contained an ion scavenger (see comparison of results of Examples 9, 31 and 32, etc.).

It was confirmed that the effect of the present invention is more excellent when the ion scavenger of the composition is a composite of magnesium and aluminum or a composite of zirconium and bismuth (comparison with Examples 9 and 31). , Comparison of the results of Examples 24, 33-36, etc.).

The epoxy compound is a polyhydroxybenzene-type glycidyl ether, a bisphenol F-type glycidyl ether, a rod-shaped compound, a phenoxy resin, or a disk-shaped epoxy compound because the heat-conducting material formed is more excellent in suppressing moisture absorption and solder heat resistance. It was confirmed that it was preferable to include a compound (see Examples 5, 11 to 20 comparison of results, etc.).
Further, when the epoxy compound contains an epoxy compound having a triazine ring as the central ring, it has a phenol compound having a triazine skeleton and a triazine skeleton because the formed heat conductive material is more excellent in suppressing moisture absorption and solder heat resistance. It was confirmed that the total content of the epoxy compound is preferably 5 to 80% by mass with respect to the total content of the total phenol compound and the total epoxy compound (results of Examples 10 and 20). See comparison etc.).

When the molecular weight of the curing accelerator of the composition is 250 or more, it is confirmed that the solder heat resistance II is more excellent, and when the molecular weight of the curing accelerator of the composition is 430 or more, the solder heat resistance II is further improved. It was confirmed to be excellent (see comparison of results of Examples 2 to 5, 24, 29, 30, 59 to 75, etc.).

<< Test Y >>
Test Y (Example 76 or later) was carried out based on the conditions and procedures as shown below.

[Preparation of composition]
After mixing the solvent (cyclopentanone), phenol compound, epoxy compound, ion scavenger to be used as desired, specific compound (maleimide compound), and curing accelerator in this order, an inorganic substance or a surface-modified inorganic substance was added. .. The obtained mixture was treated with a rotation revolution mixer (manufactured by THINKY, Awatori Rentaro ARE-310) for 5 minutes to obtain a composition (curable composition) of each example.

Here, the amount of the solvent added was such that the solid content concentration of the composition was 42.5% by volume (in the range of 52 to 58% by mass on a mass basis).
The solid content concentration of the composition was adjusted for each composition within the above range so that the viscosities of the compositions were about the same.
The total content of the epoxy compound and the phenol compound is the amount shown in the "total amount (% by mass)" column in Table 2 with respect to the total solid content of the composition, and the total number of epoxy groups of the epoxy compound. And the ratio to the total number of hydroxyl groups of the phenol compound was adjusted to be the ratio shown in the "[epoxide / phenol] functional group ratio" column in Table 2.
The composition of the solid content of the composition of Example 76 in Test Y is the same as the composition of the solid content of the composition of Example 11 in Test X, respectively.

[evaluation]
[Evaluation of thermal conductivity, Tg (heat resistance), insulation]
In Test X, the same methods and evaluation criteria as shown in [Evaluation method of thermal conductivity], [Evaluation of Tg (heat resistance)], and [Evaluation of insulation] were used for each Example of Test Y. The composition was also tested and evaluated for thermal conductivity, Tg (heat resistance), and insulation, respectively.

[Evaluation of handleability (preservation over time)]
A semi-cured sheet (semi-cured film) using the composition of each example of Test Y was prepared by the method shown in [Preparation of semi-cured sheet (semi-cured film)] in Test X.
The PET film was peeled off from the obtained semi-cured sheet and allowed to stand at room temperature (25 ° C.) for 1 hour immediately after production.
The semi-cured sheet after standing was cut into strips of 5 cm × 10 cm to prepare a sample for bending test. The obtained sample was further allowed to stand at room temperature (25 ° C.) for 23 hours.
The sample after standing was subjected to a bending test using a cylindrical mandrel testing machine (manufactured by Cortec Co., Ltd.) according to the method described in JIS K 5600-5-1. Using cylindrical mandrel with diameters of 25 mm, 20 mm, and 16 mm, respectively, from the diameter of the mandrel used for the bending test when the sample was broken or broken, one day after preparation based on the following evaluation criteria. The handleability of the semi-cured sheet (after 24 hours) was evaluated.
The shorter the diameter of the mandrel used when the sample is damaged, the better the handling of the semi-cured sheet after storage over time.
The diameter of the mandrel at the time of breakage was classified according to the following criteria, and the handleability (preservability over time) was evaluated.
A +: No damage at 25 mm, 20 mm and 16 mm A: No damage at 25 mm and 20 mm, damage at 16 mm B: No damage at 25 mm, damage at 20 mm and 16 mm C: Damage at 25 mm, 20 mm and 16 mm

[result]
Table 2 is shown below.
Table 2 shows the composition of the solid content and the test results of the composition in each example.
In the "Type" column of the epoxy compound in the table, the mass ratio of the content of each epoxy compound is shown in the form of "X / Y" when a plurality of types of epoxy compounds are used.
In the table, the "Viscosity (mPa · s, 25 ° C.)" column indicates the viscosity of the used epoxy compound at 25 ° C. The method for measuring the viscosity is as shown in the specification.
In the "[epoxide / phenol] functional group ratio" column, the ratio of the total number of epoxy groups of the epoxy compound to the total number of hydroxyl groups of the phenol compound in the composition (total number of the epoxy groups / total of the hydroxyl groups). Number) is shown.

Also in Test Y, it was confirmed that if the composition of the present invention is used, a heat conductive material having excellent heat conductivity and heat resistance can be formed. It was also confirmed that the heat conductive material formed by using the composition of the present invention has excellent insulating properties.

Further, it was confirmed that when the epoxy compound contains a low-viscosity epoxy compound, the handling property of the semi-cured film formed by using the composition is more excellent.
(See comparison of results of Examples 80 and 91, etc.)

In that the heat resistance (Tg) of the obtained heat conductive material is more excellent, the epoxy compound is an epoxy compound having an aromatic ring group, or is represented by the general formula (E3) in which X is an integer of 1 to 3. It was confirmed that the epoxy compound to be used is preferable, and the epoxy compound having an aromatic ring group is more preferable.
(See Comparison of Results of Examples 77, 79, 88, 90, Comparison of Results of Examples 80, 89, 91, etc.).

It was confirmed that the content of the maleimide compound is preferably 6% by mass or more with respect to the total solid content of the composition from the viewpoint of more excellent thermal conductivity and / or insulating property of the obtained thermal conductive agent material. (See Comparison of Results in Examples 77, 78, etc.).

The total number of epoxy groups contained in the epoxy compound relative to the total number of hydroxyl groups contained in the phenol compound in that the handling property of the semi-cured film and / or the heat resistance (Tg) of the obtained heat conductive material is more excellent. The ratio to the number (number of epoxy groups / number of hydroxyl groups) is preferably 1.1 / 1.0 to 3.0 / 1.0, and 1.2 / 1.0 to 2.0 / 1. It was confirmed that the value is more preferably 1.0, and the value is further preferably 1.3 / 1.0 to 1.8 / 1.0.
(See Comparison of Results of Examples 85-87, Comparison of Results of Examples 77 and 84, Comparison of Results of Examples 78 and 85, etc.).

Claims

Phenolic compounds and
One or both of a maleimide compound having one or more maleimide groups and a cyanate compound having one or more cyanate groups.
Inorganic, including
A curable composition in which the inorganic substance contains an inorganic nitride.
Contains the maleimide compound
The curable composition according to claim 1, wherein the maleimide compound is a compound represented by the general formula (1).

In the general formula (1), m represents 0 or 1.
n represents 0 or 1.
R 1 and R 2 independently represent a hydrogen atom or a substituent.
L 1 represents a divalent linking group.
The curability according to claim 2, wherein in the general formula (1), m represents 1, n represents 1 , and the divalent linking group represented by L1 has 3 to 15 carbon atoms. Composition.
Contains the maleimide compound
The curable composition according to any one of claims 1 to 3, wherein the maleimide compound has two maleimide groups.
The curable composition according to any one of claims 1 to 4, wherein the inorganic substance contains boron nitride.
The curable composition according to claim 5, wherein the boron nitride contains aggregated boron nitride having an average particle size of 20 μm or more.
In addition, it contains a surface modifier and
The curable composition according to claim 5 or 6, wherein the boron nitride constitutes a surface-modified boron nitride together with the surface modifier adsorbed on the surface of the boron nitride.
The curable composition according to any one of claims 1 to 7, further comprising an epoxy compound.
Contains the maleimide compound and
The curable composition according to claim 8, wherein the epoxy compound contains an epoxy compound having a viscosity at 25 ° C. of less than 1000 mPa · s.
Contains the maleimide compound and
The ratio of the total number of hydroxyl groups contained in the phenol compound to the total number of epoxy groups contained in the epoxy compound in the curable composition is 1.2 / 1.0 to 2.0 / 1. The curable composition according to claim 8 or 9, which is 0.0.
The invention according to any one of claims 8 to 10, wherein the phenol compound satisfies at least one of the requirements that the phenol compound contains a phenol compound having a triazine skeleton and the epoxy compound contains an epoxy compound having a triazine skeleton. Curable composition.
The curable composition according to any one of claims 1 to 11, further comprising a curing accelerator.
The curable composition according to claim 12, wherein the curing accelerator contains a compound containing a phosphorus atom.
The curable composition according to claim 12 or 13, wherein the curing accelerator contains a phosphonium salt.
The curable composition according to any one of claims 12 to 14, wherein the curing accelerator has a molecular weight of 430 or more.
The curable composition according to claim 12, wherein the curing accelerator contains a compound represented by the general formula (P3).

In the general formula (P3), R p31 to R p34 each independently represent a phenyl group which may have a substituent.
The curable composition according to any one of claims 1 to 16, further comprising an ion scavenger.
A heat conductive material obtained by curing the curable composition according to any one of claims 1 to 17.
A heat conductive sheet made of the heat conductive material according to claim 18.
The heat conductive sheet according to claim 19, wherein the mass change rate obtained by the following formula is less than 1.0%.
Mass change rate (%) = (W2-W1) / W1 × 100
W1: Mass of the heat-conducting sheet in a dry state after being dried in an environment of 120 ° C. for 2 hours W2: Moisture absorption after the heat-conducting sheet in a dry state is placed in an environment of 85 ° C. and 85 RH% for 24 hours. The mass of the heat-conducting sheet in the state
A device with a heat conductive layer having a device and a heat conductive layer including the heat conductive sheet according to claim 19 or 20 arranged on the device.