WO2021230002A1

WO2021230002A1 - Curable composition, thermally conductive material, thermally conductive sheet, device with thermally conductive layer, and compound

Info

Publication number: WO2021230002A1
Application number: PCT/JP2021/015744
Authority: WO
Inventors: 誠一人見; 大介林; 慶太高橋; 輝樹新居; 信小澤
Original assignee: 富士フイルム株式会社
Priority date: 2020-05-15
Filing date: 2021-04-16
Publication date: 2021-11-18
Also published as: TW202144449A; JPWO2021230002A1; JP7440626B2

Abstract

The present invention provides a curable composition capable of giving thermally conductive materials having excellent thermal conductivity. Also provided are a thermally conductive material, a thermally conductive sheet, a device with a thermally conductive layer, and a compound, which each relate to the curable composition. This curable composition comprises a phenol compound, an epoxy compound, a curing accelerator, and an inorganic substance, wherein the phenol compound is a specific phenol compound satisfying requirement 1 and/or requirement 2 and the content of the inorganic substance exceeds 10 mass% based on all the solid components.　Requirement 1: To be a compound represented by general formula (Y).　Requirement 2: To be a phenol compound having a triazine skeleton and having an aromatic ring group that includes a phenolic hydroxyl group and a substituent arranged in an ortho position to the phenolic hydroxyl group.

Description

Curable compositions, heat conductive materials, heat conductive sheets, devices with heat conductive layers, compounds

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

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 composition containing a predetermined epoxy resin, a curing agent, and a filler under predetermined conditions as an epoxy resin composition having excellent handleability in a B stage state and thermal conductivity of a cured product. Things are open to the public.

International Publication No. 2017/145413

The present inventors examined the epoxy resin composition described in Patent Document 1, and found that there is room for improvement in the thermal conductivity of the obtained cured product.

Therefore, it is an object of the present invention to provide a curable composition capable of providing a heat conductive material having excellent heat conductivity.
Another object of the present invention is to provide a heat conductive material, a heat conductive sheet, a device with a heat conductive layer, and a compound for 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]
A curable composition comprising a phenol compound, an epoxy compound, a curing accelerator, and an inorganic substance.
The phenolic compound satisfies at least one of Requirement 1 and Requirement 2.
A curable composition in which the content of the inorganic substance is more than 10% by mass with respect to the total solid content.
Requirement 1: A compound represented by the general formula (Y).
Requirement 2: A phenol compound having a triazine skeleton and having an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group.

In the general formula (Y), my represents an integer of 0 or more.
^RY1 and ^RY2 each independently represent an aromatic ring group having a phenolic hydroxyl group and a substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group.
^LY1 and ^LY2 independently represent -C ( ^RY5 ) ( ^RY6)-or- CO-, respectively.
^RY3 to ^RY6 independently represent a hydrogen atom or a substituent.
[2]
The curable composition according to [1], wherein the temperature at which the exothermic peak is detected is 140 ° C. or higher when the semi-curable sheet formed by using the curable composition is measured by a differential scanning calorimeter. ..
[3]
The curable composition according to [1] or [2], wherein the epoxy compound has a molecular weight of 300 or more.
[4]
The curable composition according to any one of [1] to [3], wherein the inorganic substance contains aggregated boron nitride having an average particle size of 20 μm or more.
[5]
The curable composition according to any one of [1] to [4], wherein the phenol compound contains a compound represented by the general formula (Z).

In the general formula (Z), r represents an integer of 0 or more.
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.
L represents a divalent organic group.
E ¹ to E ⁶ independently represent a single bond, -NH-, or -NR-. R represents a substituent.
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.
X ¹ to X ⁴ each independently represent an aromatic ring group having a phenolic hydroxyl group.
However, at least one of k X ¹ , l X ² , r × m X ³ , and n X ⁴ is an ortho of a phenolic hydroxyl group and a phenolic hydroxyl group. Represents an aromatic ring group having a substituent arranged at the position.
[6]
The curable composition according to any one of [1] to [5], wherein the phenol compound contains a compound represented by the general formula (Z1).

In the general formula (Z1), r represents an integer of 0 or more.
L represents a divalent organic group.
R ^Z represents a hydrogen atom or a substituent.
Provided that at least one of ^{R Z} which in the general formula (Z1) (3 + r) pieces there is a substituent.
Further, at least one of ^{R Z} which in the general formula (Z1) (3 + r) pieces there is a hydrogen atom.
[7]
The curable composition according to any one of [1] to [6], wherein the phenol compound contains a compound represented by the general formula (Z2).

In the general formula (Z2), R ^Z represents a hydrogen atom or a substituent.
However, at least one of the two existing R ^{Zs represents a substituent.}
[8]
The curable composition according to any one of [1] to [7], wherein the curing accelerator contains a compound containing a phosphorus atom.
[9]
The curable composition according to any one of [1] to [8], wherein the curing accelerator contains a phosphonium salt.
[10]
A heat conductive material obtained by curing the curable composition according to any one of [1] to [9].
[11]
A heat conductive sheet made of the heat conductive material according to [10].
[12]
A device with a heat conductive layer having a device and a heat conductive layer including the heat conductive sheet according to [11] arranged on the device.
[13]
A compound represented by the general formula (Z).

In the general formula (Z), r represents an integer of 0 or more.
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.
L represents a divalent organic group.
E ¹ to E ⁶ independently represent a single bond, -NH-, or -NR-. R represents a substituent.
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.
X ¹ to X ⁴ each independently represent an aromatic ring group having a phenolic hydroxyl group.
However, at least one of k X ¹ , l X ² , r × m X ³ , and n X ⁴ is an ortho of a phenolic hydroxyl group and a phenolic hydroxyl group. Represents an aromatic ring group having a substituent arranged at the position.
[14]
The compound according to [13], which is represented by the general formula (Z1).

In the general formula (Z1), r represents an integer of 0 or more.
L represents a divalent organic group.
R ^Z represents a hydrogen atom or a substituent.
Provided that at least one of ^{R Z} which in the general formula (Z1) (3 + r) pieces there is a substituent.
Further, at least one of ^{R Z} which in the general formula (Z1) (3 + r) pieces there is a hydrogen atom.
[15]
The compound according to [13] or [14], which is represented by the general formula (Z2).

In the general formula (Z2), R ^Z represents a hydrogen atom or a substituent.
Provided that at least one of the two existing R ^Z in the general formula (Z2) represents a substituent.

According to the present invention, it is possible to provide a curable composition capable of providing a heat conductive material having excellent heat conductivity.
Further, according to the present invention, it is possible to provide a heat conductive material, a heat conductive sheet, a device with a heat conductive layer, and a compound related to the curable composition.

Hereinafter, the curable composition, the heat conductive material, the heat conductive sheet, the device with the heat conductive layer, and the compound 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 an acryloyl group and a methacryloyl group". Further, the description of "(meth) acrylamide group" means "either one or both of an acrylamide group and a methacrylamide group".

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, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO 3 _H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl 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 Nookishi group _(-OPO 3 H _(aryl)) and its conjugated base group, a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group and an 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 moiety 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 a curable composition containing a phenol compound, an epoxy compound, a curing accelerator, and an inorganic substance.
The phenolic compound satisfies at least one of Requirement 1 and Requirement 2.
A curable composition in which the content of the inorganic substance is more than 10% by mass with respect to the total solid content.
Requirement 1: A compound represented by the general formula (Y) described later.
Requirement 2: A phenol compound having a triazine skeleton and having an aromatic ring group having a phenolic hydroxyl group and a substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group.

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.
The phenol compound contained in the composition of the present invention (hereinafter, also referred to as “specific phenol compound”) has a phenolic hydroxyl group having a substituent at the ortho position as a phenolic hydroxyl group, and has a predetermined structure. .. Due to these characteristics of the specific phenolic compound, the cured product formed from the composition can have a rigid structure, resulting in faster heat transfer in the cured product, resulting in formation. It is believed that the thermal conductivity of the heat-conducting material is improved.
In addition, the composition of the present invention has good storage stability after being formed into a semi-cured film, has a high dielectric breakdown voltage of the prepared heat conductive material, and is adhered via the prepared heat conductive material. The peel strength between the materials can also be improved.
Hereinafter, excellent in the above-mentioned thermal conductivity, the above-mentioned storage stability, the above-mentioned dielectric breakdown voltage, and / or the above-mentioned peel strength is also referred to as an excellent effect of the present invention.

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 specific phenol compound that satisfies at least one of the following requirements 1 and 2.
The specific phenol compound may satisfy only the following requirement 1, only the following requirement 2, or both the following requirement 1 and the following requirement 2.
Requirement 1: A compound represented by the general formula (Y).
Requirement 2: A phenol compound having a triazine skeleton and having an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group.

<Requirement 1>
The specific phenol compound satisfying the requirement 1 is a compound represented by the general formula (Y).

When a plurality of groups represented by the same reference numeral exist in the above general formula (Y), the plurality of groups represented by the same reference numeral may be the same or different unless otherwise specified. ..

In the general formula (Y), my represents an integer of 0 or more.
My is preferably an integer of 0 to 10, more preferably an integer of 0 to 1, and even more preferably 1.

In the general formula (Y), ^RY1 and ^RY2 each independently represent an aromatic ring group having a phenolic hydroxyl group and a substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group.
That is, the aromatic ring group represented by R ^Y1 and R ^Y2, having a phenolic hydroxyl group is present substituents having 1 to 6 carbon atoms in the ortho position.
The "phenolic hydroxyl group having a substituent having 1 to 6 carbon atoms at the ortho position" is a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring (preferably an aromatic hydrocarbon ring, more preferably a benzene ring). It refers to a hydroxyl group in which a substituent having 1 to 6 carbon atoms is present in one or both of the positions (ortho positions) adjacent to the hydroxyl group in the aromatic ring.
The aromatic ring group may have one or more (for example, 1 to 3) "phenolic hydroxyl groups having a substituent having 1 to 6 carbon atoms at the ortho position" and "1 carbon number at the ortho position". It may or may not have a phenolic hydroxyl group other than the "phenolic hydroxyl group in which the substituents of to 6 are present".
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 substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group may be present at at least one of the ortho positions of the phenolic hydroxyl group, and may be present at both of them.
The number of carbon atoms in the substituent having 1 to 6 carbon atoms is 1 to 6, preferably 1 to 4, and more preferably 1.
The substituent having 1 to 6 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
The alkyl group may be linear or branched. It is also preferable that the alkyl group is unsubstituted.

^RY1 and ^RY2 (that is, an aromatic ring group having a phenolic hydroxyl group and a substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group) are independently represented by the general formula (P0). It is preferable that it is a group to be used.

In the general formula (P0), ^RP1 to ^RP5 each independently represent a hydrogen atom or a substituent.
^However, one of R P1 ^{~ R P5} is a bond position ^and one or both of ^{R P1} and ^{R P5} is a substituent of the carbon atoms 1-6.

In ^RP1 and ^RP5 , when one is a substituent having 1 to 6 carbon atoms and the other one is other than the substituent having 1 to 6 carbon atoms, the other one is a hydrogen atom. It is also preferable.
It is also preferable that any one of ^RP2 to ^{RP4 is a bonding position.}
When ^{one or more (for example, 1 to 3) of RP2} to ^RP4 are substituents, it is also preferable that the substituent is a substituent having 1 to 6 carbon atoms.

In the general formula (Y), ^RY3 represents a hydrogen atom or a substituent.
^RY3 preferably represents a hydrogen atom or a hydroxyl group.
When a ^{plurality of RY3s} are present, it ^{is preferable that at least one RY3} represents a hydroxyl group, and it is more preferable that all ^RY3s represent a hydroxyl group.

The general formula (Y) and ^RY4 represent a hydrogen atom or a substituent.
The ^RY4 is preferably a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkoxy group, or an alkoxycarbonyl group.
The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group may or may not have a substituent.
The alkyl group portion of the alkoxy group and the alkyl group portion of the alkoxycarbonyl group are the same as those of the alkyl group.
The phenyl group may or may not have a substituent.
R ^{^Y4,} relative to the hydroxyl group ^{(R Y3)} of the benzene ring ^{group R Y4} are attached may have, preferably attached at the para-position.

In the general formula (Y), ^LY1 and ^LY2 independently represent -C ( ^RY5 ) ( ^RY6)-or- CO-, respectively.
^RY5 and ^RY6 each independently represent a hydrogen atom or a substituent.
^RY5 and ^RY6 are each independently preferably a hydrogen atom, a hydroxyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group may or may not have a substituent.
The alkyl group portion of the alkoxy group and the alkyl group portion of the alkoxycarbonyl group are the same as those of the alkyl group.
The phenyl group may or may not have a substituent. For example, when it has a substituent, it may have 1 to 3 hydroxyl groups.
L ^Y1 and ^{L Y2} are each _{independently, -CH 2 -, - CH (} OH) -, or, -CO- are preferable.

The specific phenol compound satisfying Requirement 1 may have a hydroxyl group other than "a phenolic hydroxyl group having a substituent having 1 to 6 carbon atoms at the ortho position". However, the ratio of "phenolic hydroxyl group having a substituent having 1 to 6 carbon atoms at the ortho position" among all the hydroxyl groups of the specific phenol compound satisfying Requirement 1 [(substituent having 1 to 6 carbon atoms at the ortho position). The number of phenolic hydroxyl groups in which is present / the number of total hydroxyl groups of the specific phenol compound) × 100] is preferably 30 to 100%, more preferably 50 to 100%, still more preferably 65 to 100%.

<Requirement 2>
The specific phenol compound satisfying Requirement 2 is a phenol compound having a triazine skeleton and having an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group.
By "having a triazine skeleton", a specific phenolic compound satisfying Requirement 2 means having one or more (for example, 1 to 5) triazine ring groups in the compound.

The specific phenol compound satisfying Requirement 2 has "an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group".
In other words, the specific phenol compound satisfying Requirement 2 has an aromatic ring group, and the aromatic ring group has a phenolic hydroxyl group in which a substituent is present at the ortho position.
The "phenolic hydroxyl group having a substituent at the ortho position" is a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring (preferably a benzene ring), and is a position (ortho) adjacent to the hydroxyl group in the aromatic ring. A hydroxyl group in which a substituent (preferably an organic group, more preferably a substituent having 1 to 6 carbon atoms) is present in one or both of the positions).
The aromatic ring group may have one or more (for example, 1 to 3) "phenolic hydroxyl groups having a substituent at the ortho position", and "a phenolic hydroxyl group having a substituent at the ortho position". It may or may not have a phenolic hydroxyl group other than.
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 substituent arranged at the ortho position of the phenolic hydroxyl group may be present at at least one of the ortho positions of the phenolic hydroxyl group, and may be present at both of them.
The substituent arranged at the ortho position of the phenolic hydroxyl group is preferably an organic group, and more preferably a substituent having 1 to 6 carbon atoms.
The "substituent having 1 to 6 carbon atoms" is the same as the "substituent having 1 to 6 carbon atoms" described in the description of Requirement 1.
The specific phenol compound satisfying Requirement 2 has one aromatic ring group (preferably a group represented by the above general formula (P0)) having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group. It is preferable to have the above, more preferably 2 or more, further preferably 2 to 12, and particularly preferably 4 to 8.

The specific phenol compound satisfying Requirement 2 is preferably a compound represented by the general formula (Z). The specific phenol compound preferably contains a compound represented by the general formula (Z), and the specific phenol compound may be the compound itself represented by the general formula (Z). The content of the compound represented by the general formula (Z) 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 specific phenol compound. ..

In the above general formula (Z), when a plurality of groups represented by the same reference numeral exist, 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.
Incidentally, there is r is 2 or more, if the value of m that there are a plurality are different, the value of m in m + 1-valent organic group represented by B ³ indicates the number of X ³ to which the B ³ binds m 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 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 number which may have a substituent may be used. Examples thereof include one or more hydrocarbons selected from the group consisting of 3 to 20 aliphatic rings and an aromatic ring having 3 to 20 carbon atoms which may have a substituent. Further, for the above 1 or more hydrocarbons, the group further ^{consists of -O-, -S-, -CO-, -NR N-} (RN is a hydrogen atom or a substituent), and -SO _2-. Hydrocarbons may be a combination of one or more of the selected divalent linking groups.
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 existing m (that is, r × m) and n is 2 or more, preferably an integer of 2 to 12, and more preferably an integer of 4 to 8. preferable.
Independently, k, l, m, and n are preferably 0 to 5, and more preferably 1 to 2.
For example, k is preferably 1 or more (more preferably 1 to 2), l is preferably 1 or more (more preferably 1 to 2), and m is 1 or more (more preferably 1 to 2). It is preferable that n is 1 or more (more preferably 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.
The organic group may have, for example, a divalent aromatic ring group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, and a substituent. divalent aliphatic cyclic group, -O -, - S -, - N (R N) - , or -CO-, and, a group combining thereof.
R ^N represents a substituent. The substituents represented by R ^N, e.g., like a linear or branched alkyl group having 1 to 5 carbon atoms.
Further, examples of the substituent which the aromatic ring group, the aliphatic hydrocarbon group and the aliphatic ring group may have include a linear or branched alkyl group having 1 to 5 carbon atoms. Can be mentioned.

Examples of the aromatic ring group include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a monocyclic aromatic ring group such as a benzene ring group; a naphthalene ring group, and a polycyclic aromatic ring group such as an anthracene ring group; Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include a monocyclic aromatic ring group such as a furan ring group, a pyrrole ring group, a thiophene ring group, a pyridine ring group, and a thiazole ring group; a benzothiazole ring. Examples include a polycyclic aromatic ring group such as a group, a carbazole ring group, and an indole ring group;

Examples of the 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 methylhexylene group. , And a heptylene group and the like.

Examples of the aliphatic ring group include a cyclohexane ring group, a cycloheptane ring group, a norbornane ring group, and an adamantane ring group.

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

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. Specifically, ^"- E 3 -C-" is that, and "- ^{C-E 4} -" is preferably. The C (carbon atom) is an atom constituting L. 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.

However, in the general formula (Z), at least one of k existing X ¹ , l existing X ² , r × m existing X ³ and n existing X ⁴ is phenolic. Represents an aromatic ring group having a hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group. The value of m in "r × m" is an average value of m that may exist in a plurality of values.
^{In other words, of the "aromatic ring groups having phenolic hydroxyl groups" represented by any of X 1} to X ⁴ existing (k + l + r × m + n), at least one is "ortho-phenolic hydroxyl group and phenolic hydroxyl group". Represents an aromatic ring group having a substituent arranged at the position.
^{Among the "aromatic ring groups having a phenolic hydroxyl group" represented by any of X 1} to X ⁴ existing (k + l + r × m + n), "arranged at the ortho position of the phenolic hydroxyl group and the phenolic hydroxyl group". Ratio of "aromatic ring groups having a substituent" [(number of "aromatic ring groups having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" / (k + l + r × m + n)) X present number) × 100] of the "aromatic ring group having a phenolic hydroxyl group" represented by any one of the ^{1 ~} X ⁴ is preferably 30% or more, more preferably 50% or more, more preferably 65% or more. The upper limit is preferably 100% or less, more preferably 90% or less, still more preferably 80% or less.
The above-mentioned "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" is, for example, the "ortho-position of the phenolic hydroxyl group and the phenolic hydroxyl group" described with respect to the description of the general formula (Y). In the "aromatic ring group having a substituent having 1 to 6 carbon atoms" arranged in, the "substituted group having 1 to 6 carbon atoms" is not particularly limited to a "hydroxyl group (may be a hydroxyl group, preferably a non-hydroxyl group)". The form replaced with is mentioned.

The "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" independently has "1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group and the phenolic hydroxyl group". It is preferably an aromatic ring group having a substituent of.
The above-mentioned "aromatic ring group having a phenolic hydroxyl group and a substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group" is the "phenolic hydroxyl group and phenolic" described with respect to the above general formula (Y). It is the same as the aromatic ring group having a substituent having 1 to 6 carbon atoms arranged at the ortho position of the hydroxyl group, and is preferably a group represented by the above general formula (P0).

In the aromatic ring group having a phenolic hydroxyl group represented by X 1 ^~ X ^4, aromatic ring other than the "aromatic ring group having a substituent located in the ortho position of the phenolic hydroxyl group and a phenolic hydroxyl group" is, 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". As a result, the symmetry of the compound as a whole is broken, the melting point of the compound is lowered, and the handleability is improved. Further, when a compound having such a form is combined with an epoxy compound to form a composition, the exothermic peak detected by measuring the composition with a DSC (differential scanning calorimetry) becomes broad (increase in half-value width or increase in half-value width). Increasing the difference between the exothermic peak temperature and the reaction start temperature). When such broadening occurs, the composition can be cured at a wide temperature and is considered to be preferable.

The specific phenol compound satisfying Requirement 2 is preferably a compound represented by the general formula (Z1). The specific phenol compound preferably contains a compound represented by the general formula (Z1), and the specific 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 specific 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.
Substituents represented by R ^Z, it is preferable, more preferably a hydrocarbon group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms that is a substituent having 1 to 6 carbon atoms Is even more preferable.
Provided that at least one of ^{R Z} which in the general formula (Z1) (3 + r) pieces there is a substituent. (3 + r) pieces presence of ^{R Z} is the percentage of ^{R Z} representing a substituent [(number of number / (3 + r) pieces present ^{R Z} of ^{R Z} representing a substituent) × 100] is 30% or more It is preferable, 50% or more is more preferable, and 65% or more is further preferable. The upper limit is preferably 90% or less, more preferably 80% or less.
At least one (for example, 1 to 2) of ^{R Z} existing in (3 + r) in the general formula (Z1) represents a hydrogen atom.
^(Preferably R ^z is a substituted ^group) R ^z in the general formula (Z1) in the benzene ring group and OH is bonded, the R ^{z (R} ^z is preferably substituted ^groups), the benzene ring is bonded It is also preferable that it exists in the para position with respect to NH.

The specific phenol compound satisfying Requirement 2 is preferably a compound represented by the general formula (Z2). The specific phenol compound preferably contains a compound represented by the general formula (Z2), and the specific 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 specific phenol compound. ..

In the general formula (Z2), R ^Z represents a hydrogen atom or a substituent.
However, at least one of the two existing R ^{Zs represents a substituent.} It is preferred that both of the two existing R ^{Zs represent substituents.}
Substituents represented by R ^Z, it is preferable, more preferably a hydrocarbon group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms that is a substituent 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.

The specific phenol compound satisfying Requirement 2 may have a hydroxyl group other than "a phenolic hydroxyl group having a substituent (preferably a substituent having 1 to 6 carbon atoms) at the ortho position". However, the ratio of "phenolic hydroxyl group having a substituent (preferably a substituent having 1 to 6 carbon atoms) at the ortho position" among all the hydroxyl groups of the specific phenol compound satisfying Requirement 2 [(the number of carbon atoms at the ortho position). The number of phenolic hydroxyl groups in which 1 to 6 substituents are present / the number of total hydroxyl groups of the specific phenol compound) × 100] is preferably 30% or more, more preferably 50% or more, still more preferably 65% or more. The above number is preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less.

The molecular weight of the specific phenol compound is preferably 225 to 2000, more preferably 225 to 1000.

The hydroxyl group content of the specific 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 specific 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.

The specific phenol compound may be used alone or in combination of two or more.
Among them, the specific phenol compound is a compound represented by the general formula (Z), and is represented by any of (k + l + r × m + n) X ¹ to X ⁴ , which is a “aromatic ring group having a phenolic hydroxyl group”. Of the above, at least one (for example, 1 to 2) is a compound which is an aromatic ring group other than "an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" (for example, general). The compound represented by the formula (Z2) is preferably contained in an amount of 10 to 100% by mass, more preferably 25 to 100% by mass, and 50 to 100% by mass based on the total mass of the specific phenol compound. Is more preferable.
In addition to the specific phenol compound, the composition of the present invention may contain a compound having a group capable of reacting with an epoxy compound described later (also referred to as “other active hydrogen-containing compound”).
The other active hydrogen-containing compound may be, for example, a phenol compound other than the specific phenol compound.
However, in the composition of the present invention, the mass ratio of the content of the other active hydrogen-containing compound to the content of the specific phenol compound is preferably 0 to 1, more preferably 0 to 0.1, and 0 to 0. 05 is more preferable.

[Epoxy compound]
The composition of the present invention comprises 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 number 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 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 a rod-like structure at least partially (a rod-like compound) and a compound having a disk-like structure at least partially. Be done.
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 phenylpyrimidins, 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 low molecular weight reactive group.
Preferred rod-shaped compounds include rod-shaped compounds represented by the following general formula (XXI).
Formula ^{^{^{^{(XXI): Q 1 -L 111}}}} -A 111 -L 113 -M-L 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.
Epoxy group of Q ¹ and Q ² may be substituted or may not have.

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 ^{^{112 -, - NR 112 -CO-}} O-, ^and, -NR ^{112 -CO-NR} 112 - is preferably a divalent linking group selected from the group consisting of. 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. Of these, a 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, thiophen-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. Acrylic group (eg, formyl group, acetyl group, etc.), alkoxycarbonyl group having 1 to 10 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), acyloxy group having 1 to 10 carbon atoms (eg, ethoxycarbonyl group, etc.). Acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like can be mentioned.
If W ¹ there are a plurality, W ¹ existing in plural numbers may each be the same or different.

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, the compound represented by the general formula (XXI), ^"Q 1 ^{-L 111} -" one or both of and ^"-L 112 -Q ^2" is, compounds replaced the diglycidyl amino group are also preferred.

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, L E2} are each independently a single bond, -CO-O-, or, -O-CO- is preferred.
When there are a plurality of ^LE2s ^{, the plurality of LE2s} may be the same or different.

In the general formula (E1), ^LE3 may independently have a single bond or a substituent, respectively, and may have a 5-membered ring or a 6-membered ring aromatic ring group or a 5-membered ring or a 6-membered ring. Represents a non-aromatic ring group of, or a polycyclic group consisting of these rings.
Examples of aromatic ring groups and non-aromatic ring group represented by L ^E3, which may have a substituent, 1,4-cyclohexane-diyl group, 1,4-cyclohexene-diyl group, 1,4 -Phenylene group, pyrimidin-2,5-diyl group, pyridine-2,5-diyl group, 1,3,4-thiadiazol-2,5-diyl group, 1,3,4-oxadiazol-2,5 Examples thereof include a diyl 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, L E3} represents a single bond, 1,4-phenylene group, or 1,4-cyclohexene-diyl group are preferable.
Substituent having a group represented by L ^E3 each independently represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or, preferably an acetyl group, an alkyl group (preferably having a carbon number of 1) Gayori 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.
If pe is the integer of 2 or more, there exist a plurality of ^{^(-L} E3 -L ^E2 -) may each be the same or different.
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 may be the same or different from each other.

Further, the compound represented by the general formula (E1), 2 pieces present "epoxy group -L E1 ^-" compound one or both of the diglycidyl aminoalkylene group (preferably diglycidyl aminomethylene group) was replaced with Is also preferable.

The rod-shaped compound preferably 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 more 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-2007-2220 and JP-A-2010-244038.

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, 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. The triphenylene structure described in 2012, 51, 7990-7793, and JP-A-7-306317, and the trisubstituted benzene structure described in JP-A-2007-2220 and JP-A-2010-240383 are terminal. Examples thereof include compounds having at least one (preferably three or more) epoxy groups.

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 heat 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 alkylene group, alkenylene group, arylene group, and two or more groups selected from the group consisting of -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 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 is Q. Combine to.
AL means an alkylene group or an alkenylene group, and AR means an arylene group.

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.
^{^{^{^{R 11, R 12, R 13}}}} , R 14, R 15 and, ^among the ^{R 16,} two or more ^may, * - ^{X 11} is -L 11 ^{-P 11,} 3 or more is ^{* -X} 11 -L ¹¹ is preferably -P ^11.
Among them, 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 a halogen atom.

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. , JP-A-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 =. Among them, -CH = is preferable for ^{A 2X} , A ^3X , and A ^{4X independently.}
R ^17X, ^{R 18X,} ^{and, R 19X} are each ^{independently,} * represents ^- _{^{(Z 21X -X 212X) n21X -L}} 21X -Q - X 211X. * 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-membered or 6-membered aromatic ring group or a 5-membered or 6-membered non-aromatic ring group.
L ^21X represents a single bond or a divalent linking group.
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.
However, the compound represented by the formula (D16) preferably does not have -NH- from the viewpoint of the stability of the epoxy group.

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. Among them, -CH = is preferable for ^{A 2} , A ³ and A ^4. In other words, it is also preferable that the central ring of the disk-shaped compound is a benzene ring.

R ^17, ^{R 18,} ^{and, R 19} are each ^{^{^{_{independently, * - X 211 - (Z}}}} 21 -X 212) n21 -L 21 -P 21, ^{^{or, * - X 221 - (Z}} 22 -X 222) representing the _n22 -Y ^22. * Represents the position of connection with the central ring.
R ^17, ^{R 18} and ^two or more of ^{R 19} ^is, * ^- X ²¹¹ - a _{^{(Z 21 -X 212) n21 -L}} 21 -P 21. From the viewpoint of thermal conductivity of the thermally conductive material is more ^excellent, R ^{17, R 18,} and ^{all R 19} ^has, * ^- X ²¹¹ - and even a _{^{(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 bonds, —O—, —CO—O—, or —O—CO— are 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 1,4-phenylene group. , 1,3-Phenylene group, and aromatic heterocyclic group.

The aromatic ring group and the non-aromatic ring group may have a substituent. The number of substituents is preferably 1 or 2, 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.

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. X ⁴ 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, X ⁴ 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.

In the case described later n22 is 1 or ^more, -X 212 ^{-L 21} - Examples of are examples of L in the above formula (D1) ~ (D15) L101 ~ L143 and the like as well.

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

Y ²² is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclically charged 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-. represents radicals substituted by O-, has the same meaning as Y ¹² in the general formula (XI), preferred ranges are also the same.

N21 and n22 each independently represent an integer of 0 to 3, and from the viewpoint of better thermal conductivity, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is more preferable.

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-2006-76992, and JP-A-2007-2220.

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)
Examples of other epoxy compounds other than the above-mentioned epoxy compounds include epoxy compounds represented by the general formula (DN).

In the general formula (DN), ^nDN represents an integer of 0 or more, preferably 0 to 5, and more preferably 1.
^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 further preferable.

Examples of other polyfunctional epoxy compounds include epoxy compounds represented by the general formula (E1).
(V-) _4- UC (-W) _U (E1)

In the general formula (E1), C represents a carbon atom.

In the general formula (E1), U represents an integer of 3 or 4.
In the general formula (E1), "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 (E1) is "VC (-W) ₃ " or "C (-W) ₄ ".

In the general formula (E1), V represents a substituent having no hydrogen atom or 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 (E1), 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-epoxy 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 (E1) 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.

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); Polyhydroxybenzene type glycidyl ether (polyhydroxybenzene type) Epoxy compound); benzenepolycarboxylic acid type glycidyl ester (benzenepolycarboxylic acid type epoxy compound); trisphenol methane type epoxy compound; and phenoxy resin. 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.

It is preferable to determine the epoxy compound to be used in consideration of each performance to be realized in the composition.
For example, when the epoxy compound has an aromatic ring group (benzene ring or the like), the heat conductivity of the heat conductive material is more excellent.
When an epoxy compound having a flexible structure or excellent moldability is used, the storage stability of the semi-cured sheet formed from the composition is more excellent. Examples of such an epoxy compound include a bisphenol F type epoxy compound, an epoxy compound represented by the general formula (E1), and an epoxy compound having a diglycidylamino group.
When the epoxy compound has liquidity, the thermal conductivity and / or peel strength of the heat conductive material formed from the composition is more excellent.
Further, when the epoxy compound is an epoxy compound represented by the general formula (DN), the thermal conductivity and / or peel strength of the heat conductive material formed from the composition is more excellent.

The epoxy compound may be used alone or in combination of two or more.
By using two or more kinds of epoxy compounds, it is easy to adjust the balance of the performance of the composition.
For example, when a bisphenol F type epoxy compound and a phenoxy resin are used, when a bisphenol F type epoxy compound and a phenol novolac type epoxy compound are used, and when a polyhydroxybenzene type epoxy compound and a phenol novolac type epoxy compound are used. In such cases, the balance of performance of the composition becomes better.

The ratio of the number of epoxy groups contained in the epoxy compound to the number of phenolic hydroxyl groups contained in the total phenol compound in the composition (number of epoxy groups / number of phenolic hydroxyl groups) is 40/60 to 60/40. Preferably, 45/55 to 55/45 is more preferable.
That is, the ratio of the content of the total 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.
The total phenol compound referred to here is intended to be both a specific phenol compound and other phenol compounds.

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 preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and even more preferably 45/55 to 55/45.

The total content of the epoxy compound and the total phenol compound in the composition is preferably 5 to 90% by mass, more preferably 10 to 50% by mass, and 15 to 40% by mass with respect to the total solid content of the composition. % Is more preferable.
The total 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.

[Hardening accelerator]
The composition of the present invention contains a curing accelerator.
Examples of the curing accelerator include trisorthotrilphosphine, triphenylphosphine, boron trifluoride amine complex, and the compounds described in paragraph 0052 of JP2012-67225A. In addition, tetraphenylphosphonium tetraphenylborate (TPP-K), tetraphenylphosphonium tetra-p-tolylborate (TPP-MK), tetra-n-butylphosphonium laurate (TBP-LA), bis (tetra-n-butylphosphonium) ) Pyromeritate and onium salt-based curing accelerators such as quaternary phosphonium-based compounds (phosphonium salts) such as bis (naphthalen-2,3-dioxy) phenylsilicate adduct of tetraphenylphosphonium 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-2004-43405 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-2014-5382.
Among them, the curing accelerator preferably contains a compound containing a phosphorus atom, and more preferably contains a phosphonium salt. The curing accelerator may be a compound containing a phosphorus atom or a phosphonium salt itself. 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.

[Inorganic substances]
The composition of the present invention contains an inorganic substance.
As the inorganic substance, any inorganic substance conventionally used for the inorganic filler of the heat conductive material may be used. The inorganic substance preferably contains an inorganic nitride or an inorganic oxide, and more preferably at least an inorganic nitride, because the heat conductive material is more excellent in thermal conductivity and insulating property.

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, scaly shape, agglomerated shape, and indefinite shape.

Examples of the inorganic oxide include zirconium oxide (ZrO ₂ ), titanium oxide (TIO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO, Fe _3). O ₄ ), copper oxide (CuO, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In _2). O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi ₂₎ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), germanium oxide (GeO ₂ , GeO), lanthanum oxide (La ₂ O ₃ ), and Examples thereof include ruthenium oxide (RuO _2).
As the above-mentioned inorganic oxide, only one kind may be used, or two or more kinds may be used.
The inorganic oxide is preferably titanium oxide, aluminum oxide, 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.

Examples of the inorganic nitride include boron nitride (BN), carbon nitride (C ₃ N ₄ ), silicon nitride (Si ₃ N ₄ ), gallium nitride (GaN), indium nitride (InN), and 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), Niob Nitride (NbN), Tantal Nitride (TaN), Titanium Nitride (TiN), Tungsten Nitride (W ₂ N), Tungsten Nitride (WN ₂ ), Yttrium 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.

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.

As the inorganic substance, only one kind may be used, or two or more kinds may be used.
The inorganic substance preferably contains at least one of an inorganic nitride and an inorganic oxide, and more preferably contains at least an inorganic nitride. It may contain both inorganic nitrides and inorganic oxides.
The inorganic nitride preferably contains at least one of boron nitride and aluminum nitride, more preferably at least boron nitride, and even more preferably at least agglomerated 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) in the inorganic substance is preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and 80 to 100% by mass with respect to the total mass of the inorganic substance. % Is more preferable.
As the inorganic oxide, aluminum oxide is preferable.

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).

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, further preferably boron nitride, and particularly preferably agglutinating boron nitride.
The inorganic substance Y is preferably an inorganic nitride or an inorganic oxide, more preferably boron nitride or aluminum oxide.
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.

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 compound 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 10% by mass or more, preferably 40% 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. The upper limit is less than 100% by mass, preferably 95% by mass or less.

[Surface modifier]
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 coordination 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 monolayer 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 term "surface-modified inorganic substance" means an inorganic substance that has been surface-modified with a surface modifier, that is, a substance in which an organic substance is adsorbed on the surface of the inorganic substance.
That is, in the composition of the present invention, the inorganic substance may constitute a surface-modified inorganic substance (preferably a surface-modified inorganic nitride and / or a surface-modified inorganic oxide) in combination with the surface modifier.

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.
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.
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.

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.

[Aeon supplement]
The composition of the present invention may contain an ion catching agent.
The ionic catcher adsorbs ionic impurities in the composition or in the heat conductive material formed with the composition. This makes it possible to maintain good insulation reliability of the heat conductive material even when the heat conductive material absorbs moisture in the composition.
As the ion scavenger, a known one can be used without particular limitation. Examples of the ion trapping agent include a cation adsorbent that captures cations by ion exchange, an anion adsorbent that captures anions by ion exchange, and both cations and anions that are captured by ion exchange. Examples thereof include an inorganic ion adsorbent such as an ion catcher; a triazinethiol compound; a triazineamine compound; and a bisphenol-based reducing agent.

The inorganic ion adsorbent includes one or more oxides, oxide hydrates, and hydroxides selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. Can be mentioned.
Among them, two or more kinds of oxides, oxidative hydrates, or hydroxides selected from the group consisting of bismuth, zirconium, magnesium, and aluminum are preferable, and a three-component system of magnesium, aluminum, and zirconium is preferable. Hydrotalsite, which is a two-component oxide hydrate of oxide, bismuth and zirconium, and a hydroxide containing magnesium and aluminum, is more preferable, and hydrotalcite is even more preferable.

Examples of the triazine thiol compound include 2-dibutylamino-4,6-dimercapto-s-triazine.
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 supplement, 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-supplementing agent, the content of the ion-supplementing agent is, for example, 0.01 to 10% by mass with respect to the total solid content of the composition.
The ion catching agent 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 an amount having a solid content concentration of the composition of 20 to 90% by mass, more preferably 30 to 80% by mass, and more preferably 50 to 80% by mass. Is more preferable.
The content of the solvent is preferably 5 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.

[Fever peak]
In the composition of the present invention, when a semi-cured sheet formed using the composition is measured by a differential scanning calorimeter, the temperature at which an exothermic peak is detected (exothermic peak temperature) may be 130 ° C. or higher. It is preferably 140 ° C. or higher, more preferably 150 ° C. or higher. The upper limit of the temperature is not particularly limited, but is preferably 240 ° C. or lower, for example.
The semi-cured sheet used for measuring the exothermic peak is a semi-cured film (semi-cured film) formed by the composition. The semi-cured sheet is a sheet obtained by putting the composition in a so-called B stage state.

The semi-cured sheet is specifically defined as follows.
First of all, the uncured composition was prepared using a DSC (differential scanning calorimeter, DSC320 / 6200 manufactured by Seiko Instruments Inc., etc.) from 25 ° C to 240 ° C under the heating conditions of 10 ° C / min. Observe the reaction behavior below. This is referred to as measurement 1. If the composition to be measured contains a solvent, the solvent in the composition is removed in advance under reduced pressure before measurement 1.
Next, a sheet formed from the same composition and to be judged whether it is a semi-cured sheet or not (judgment target sheet) is similarly subjected to DSC from 25 ° C. to 240 ° C. at 10 ° C./. Observe the reaction behavior under the warming condition of the minute. This is referred to as measurement 2.
Then, the total area of the exothermic peak detected in the measurement 1 is taken as 100%, and the ratio of the total area of the exothermic peak detected in the measurement 2 is obtained as N%. When (100-N)% is set as the reaction rate of the judgment target sheet and the reaction rate is 1% or more and 50% or less, it is judged that the judgment target sheet used for the measurement 2 is a semi-cured sheet.
The method for forming the semi-cured sheet will be described later in detail in the method for curing the composition.

When a plurality of heat generation peaks are present on the semi-cured sheet, the heat generation peak temperature at the substantial heat generation peak existing on the lowest temperature side is defined as the heat generation peak temperature of the semi-cured sheet.
The above-mentioned "substantial heat generation peak" means a heat generation peak that occupies an area of 10% or more with respect to the total area (100%) of the heat generation peak of the semi-cured sheet existing between 25 ° C. and 240 ° C. do.

In the composition of the present invention, it is also preferable that the exothermic peak detected when the uncured sheet formed by using the composition is measured by DSC is broad.
The uncured sheet is, for example, a sheet obtained by removing the solvent when the composition contains a solvent, and is a so-called A-stage sheet (film).
Further, the exothermic peak is broad means that the half width of the exothermic peak is large and / or the difference between the temperature of the exothermic peak and the reaction start temperature is large.
When the composition has such characteristics, it is preferable in that curing of the composition and adhesion using the composition become possible in a wide temperature range, and various effect conditions can be applied.

[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 the curing treatment is performed, 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-hardened state, a further curing treatment may be carried out to complete the curing.
The curing treatment (also referred to as "semi-hardening treatment") for bringing the composition into a semi-hardening state and the curing treatment (also referred to as "main curing treatment") for completely curing 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-hardened treatment, it may be easy to adjust the film thickness of the obtained semi-hardened film and / or reduce the amount of voids in the semi-hardened film.
In the semi-hardening treatment, the semi-hardening treatment may be performed in a state where the coating films formed on different substrates are laminated, or the semi-hardening treatment may be performed without laminating the coating films. The semi-hardening 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-hardened film is further subjected to the main curing treatment.
In the main curing treatment, the semi-hardened 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-hardened films are laminated, or the main curing treatment may be performed without laminating the semi-hardened films.
Further, the main curing treatment may be carried out in a state where the semi-hardened 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 processing that may be performed during the semi-hardening 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 base material with a coating film may be passed through the roll press only once or may be passed a plurality of times.
In the semi-hardening 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.

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 home 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 sheet-shaped heat conductive material (heat conductive sheet) may be combined with another sheet-shaped support of the layer formed from the present composition.
Examples of the sheet-shaped support include a plastic film, a metal film, or a glass plate. Examples of the material of the plastic film include polyester such as polyethylene terephthalate (PET), polycarbonate, acrylic resin, epoxy resin, polyurethane, polyamide, polyolefin, cellulose derivative, and silicone. Examples of the metal film include a copper film.
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.
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.

[Compound]
The present invention also relates to compounds.
The compound of the present invention is a compound suitable for producing the composition of the present invention.
One form of the compound of the present invention is the compound represented by the above-mentioned general formula (Z), and the content thereof is as described above.
Further, another form of the compound of the present invention is a compound represented by the above-mentioned general formula (Z1), and the content thereof is as described above.
Further, another form of the compound of the present invention is a compound represented by the above-mentioned general formula (Z2), and the content thereof is as described above.

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.

[Preparation and evaluation of composition]
[Various ingredients]
The various components used in Examples and Comparative Examples are shown below.

<Phenol compound>
The phenolic compounds used in Examples and Comparative Examples are shown below.
The compounds A-1 to A-9 are specific phenol compounds. X-1 to X-4 are phenol compounds other than the specific phenol compound.

X-4: Catechol resorcinol novolak resin synthesized according to the method described in paragraphs [0215] to [0219] of International Publication No. 2017/14513.

(A-2 synthesis method)
A-2, which is a phenol compound, was synthesized according to the following scheme.

5-Amino-o-cresol (154.6 g, 1.26 mol) was added little by little to an ice-cooled mixture of cyanuric chloride (74.7 g, 0.41 mol) and 2-butanone (400 ml). bottom. Then, an aqueous solution prepared by dissolving sodium acetate trihydrate (110.2 g, 0.81 mol) in water (165 ml) was added to the above mixed solution. The mixed solution was stirred at 80 ° C. for 2 hours, cooled to room temperature, and an aqueous solution prepared by dissolving sodium carbonate (103 g, 0.97 mol) in water (596 ml) was added dropwise to the mixed solution and stirred for 30 minutes. After allowing the above mixed solution to stand still to remove the aqueous phase, the organic phase was filtered through cerite, and 150 ml of ethanol was added. Water (1.91 L) was added dropwise to the obtained organic phase while stirring, and the mixture was stirred for 2 hours, and then the precipitated crystals were collected by filtration and dried to obtain A-2.

(Synthesis method of A-3)
It is a phenol compound by the same method as the method for synthesizing A-2, except that the 5-amino-o-cresol used in the above-mentioned method for synthesizing A-2 is changed to 4-amino-2,6 dimethylphenol. A-3 was synthesized.

(A-4 synthesis method)
The phenolic compound A-4 was synthesized according to the following scheme.

5-Amino-o-cresol (117 g, 0.95 mol) was added little by little to the place where the mixed solution of cyanuric chloride (87.6 g, 0.475 mol) and 2-butanone (620 ml) was ice-cooled. Then, an aqueous solution prepared by dissolving sodium acetate trihydrate (135.8 g, 0.998 mol) in water (193 ml) was added to the above mixed solution. The mixed solution is stirred at 45 ° C. for 2 hours, cooled to room temperature, and an aqueous solution prepared by dissolving sodium carbonate (80.6 g, 0.76 mol) in water (700 ml) is added dropwise to the mixed solution and stirred for 30 minutes. bottom. After allowing the above mixed solution to stand still to remove the aqueous phase, the organic phase was filtered through cerite, and 210 ml of ethanol was added. Water (1.75 L) was added dropwise to the obtained organic phase while stirring, and the mixture was stirred for 2 hours, and then the precipitated crystals were collected by filtration and dried to obtain an intermediate of A-4.

M-trizine (37.3 g, 0.175 mol) was added to a mixed solution of A-4 intermediate (125.5 g, 0.35 mol) and 2-butanone (410 ml). Water (170 ml) was added to the above mixed solution, and the mixture was stirred at 80 ° C. for 2 hours and then cooled to room temperature. An aqueous solution prepared by dissolving sodium carbonate (29.8 g, 0.28 mol) in water (620 ml) was added dropwise to the above mixed solution, and the mixture was stirred for 30 minutes. The above mixed solution was allowed to stand to remove the aqueous phase, and then the organic phase was filtered through cerite. The obtained organic phase was distilled off with an evaporator and dissolved in 2-propanol (195 ml). The obtained solution was added dropwise to water (2.25 L), stirred for 2 hours, and then the precipitated crystals were collected by filtration and dried to obtain A-4.

(A-5 synthesis method)
A-5, which is a phenol compound, was synthesized by the same method as the method for synthesizing A-4, except that m-tridine used in the above-mentioned method for synthesizing A-4 was changed to m-phenylenediamine.

(A-8 synthesis method)
The phenolic compound A-8 was synthesized according to the following scheme.

5-Amino-o-cresol (20.7 g, 0.168 mol) was added little by little to an ice-cooled mixture of cyanuric chloride (15.5 g, 0.083 mol) and 2-butanone (75 ml). bottom. Then, an aqueous solution prepared by dissolving sodium acetate trihydrate (22.8 g, 0.168 mol) in water (32 ml) was added to the above mixed solution. After stirring the above mixed solution at 40 ° C. for 2 hours, m-aminophenol (10.1 g, 0.092 mol) was added, and the mixture was stirred at 80 ° C. for 2 hours. The mixed solution was cooled to room temperature, and an aqueous solution prepared by dissolving sodium carbonate (21.3 g, 0.20 mol) in water (134 ml) was added dropwise to the mixed solution and stirred for 30 minutes. After allowing the above mixed solution to stand still to remove the aqueous phase, the organic phase was filtered through cerite, and 34 ml of ethanol was added. Water (435 ml) was added dropwise to the obtained organic phase while stirring, and the mixture was stirred for 2 hours, and then the precipitated crystals were collected by filtration and dried to obtain A-8.

(A-9 synthesis method)
The phenolic compound A-9 was synthesized according to the following scheme.

The phenol compound A- 9 was synthesized.

<Epoxy compound>
The epoxy compounds used in Examples and Comparative Examples are shown below.
B-8, B-9, and B-11 are all compounds having a number average molecular weight of 300 or more.
B-5, B-6, and B-7 are epoxy compounds exhibiting liquid crystallinity.

<Inorganic matter>
The inorganic substances used in Examples and Comparative Examples are shown below.
・ HP-40: Aggregate boron nitride, average particle size: 40 μm, manufactured by Mizushima Ferroalloy Co., Ltd. ・ SGPS: Aggregate boron nitride, average particle size 12 μm, manufactured by Denka Co., Ltd. ・ SP-3: scaly boron nitride, average particle size : 4 μm, manufactured by Denka AA-3: aluminum oxide, average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd. AA-04: aluminum oxide, average particle size: 0.4 μm, manufactured by Sumitomo Chemical Co., Ltd.

<Hardening accelerator>
-C-1: Tris-orthotrilphosphine-C-2: Triphenylphosphine-C-3: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole)
C-4: TPP-MK (Tetraphenylphosphonium Tetra-p-Trillbolate)
C-5: TBP-LA (Tetra-n-Butylphosphonium Laurate)
C-6: Bis (tetra-n-butylphosphonium) pyromeritate

<Solvent>
Cyclopentanone was used as the solvent.

<Surface modifier>
KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.) was used as a surface modifier.

[Preparation of composition]
A mixture was prepared by blending the epoxy compound and the phenol compound of the combination shown in Table 1 below in an equivalent amount (the amount in which the number of epoxy groups of the epoxy compound and the number of hydroxyl groups of the phenol compound are equal).
After mixing the above mixture, solvent, surface modifier to be used if desired, and curing accelerator in this order, an inorganic substance was added. The obtained mixture was treated with a rotation / revolution mixer (Awatori Rentaro ARE-310, manufactured by THINKY) 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.
The total content of the epoxy compound and the phenol compound (content of the above mixture) in the composition is the amount shown in the "total amount (mass%)" column in Table 1 with respect to the total solid content of the composition. I tried to become.
The amounts of the curing accelerator, the surface modifier, the inorganic nitride, and the inorganic oxide in the composition are the amounts shown as "(mass%)" in Table 1 with respect to the total solid content of the composition, respectively. I did it.

[evaluation]
[Evaluation of thermal conductivity]
<Preparation of semi-cured sheet (semi-cured film)>
Using an applicator with a micrometer, the prepared composition was uniformly applied on the mold 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.
When the reaction rate of the semi-cured sheet was confirmed by the method described in the specification, it was confirmed that the reaction rate of the semi-cured sheet prepared using any of the compositions was 1% or more and 50% or less. rice field.

<Making a heat conductive sheet>
The obtained semi-cured sheet 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 thickness of 120 μm.

<Evaluation method>
The thermal conductivity of the obtained heat conductive sheet was measured by the following method.
(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 METTLER 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 measured thermal conductivity was classified according to the following criteria, and the thermal conductivity was evaluated.
A: 15W / m ・ K or more B: 13W / m ・ K or more and less than 15W / m ・ K C: 13W / m ・ K or less

[Measurement of exothermic peak temperature]
A semi-cured sheet was prepared in the same manner as shown in the above evaluation of thermal conductivity.
Using "DSC320 / 6200" manufactured by Seiko Instruments Inc., the reaction behavior was measured under the temperature rise condition of 10 ° C./min of the obtained semi-cured sheet, and the exothermic peak was measured by the method described in the specification. The temperature was measured.
The measured exothermic peak temperature was classified according to the following criteria and evaluated.
In each composition, the exothermic peak temperature was 220 ° C. or lower.
A: 150 ° C or higher B: 140 ° C or higher and lower than 150 ° C C: 130 ° C or higher and lower than 140 ° C D: less than 130 ° C

[Evaluation of dielectric breakdown voltage (withstand voltage)]
The breakdown voltage (withstand voltage) of the heat conductive sheet produced in the same manner as shown in the above evaluation of thermal conductivity at 23 ° C. and 65% relative humidity was measured by a withstand voltage tester (Kikusui Denshi Kogyo Co., Ltd.). ) Was used for measurement.

The measured dielectric breakdown voltage (withstand voltage) was converted into the dielectric breakdown voltage (withstand voltage) when the thickness of the heat conductive sheet was 200 μm. The converted breakdown voltage (withstand voltage) was classified according to the following criteria and evaluated.
A: 10 kV or more B: 8 kV or more and less than 10 kV C: less than 8 kV

[Evaluation of peel strength]
A semi-cured sheet (semi-cured sheet with PET film) was produced in the same manner as shown in the above evaluation of thermal conductivity.
The polyester film is peeled off from the semi-cured sheet with PET film, and the obtained semi-cured sheet is cut into strips of 20 mm × 60 mm, and the electrolytic copper foil (20 mm × 100 mm, thickness: 35 μm) and the aluminum plate (30 mm) which are the adherends are cut out. It was sandwiched between × 60 mm, thickness: 1 mm). The obtained laminate was heat-pressed under air (hot plate temperature 180 ° C., pressure 20 MPa for 5 minutes, then hot plate temperature 180 ° C., normal pressure for 90 minutes) to obtain a heat conductive sheet. An aluminum base substrate with a copper foil integrated with the adherend was obtained.
The copper foil peel strength of the obtained sample was measured by using a digital force gauge (ZTS-200N, manufactured by Imada Co., Ltd.) and a 90-degree peeling test jig (P90-200N-BB, manufactured by Imada Co., Ltd.) to JIS C 6481. It was measured according to the method for measuring the peeling strength in the normal state described in 1. The peeling of the copper foil in the peel strength test was performed at an angle of 90 ° with respect to the aluminum base substrate with the copper foil at a peeling rate of 50 mm / min.

The measured peel strength (peeling strength) was classified and evaluated according to the following criteria.
A: 5N / cm or more B: 4N / cm or more and less than 5N / cm C: less than 4N / cm

[Evaluation of handleability (preservation over time)]
A semi-cured sheet was prepared in the same manner as shown in the above evaluation of thermal conductivity, and then allowed to stand at room temperature (25 ° C.) for 1 day (24 hours).
The semi-cured sheet after standing was cut into strips of 5 cm × 10 cm to prepare a sample for a bending test. The obtained sample 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 32 mm, 25 mm, and 20 mm, respectively, from the diameter of the mandrel used for the bending test when the sample was broken or broken, half a day after preparation based on the following evaluation criteria. The handleability of the cured sheet was evaluated.
The shorter the diameter of the mandrel used when the sample broke, the better the shelf life of the semi-cured sheet.
When the bending test was performed on the semi-cured sheet immediately after production, none of the semi-cured sheets was damaged even when a mandrel having a diameter of 25 mm was used.

The diameter of the mandrel at the time of fracture was classified according to the following criteria, and the handleability (preservability over time) was evaluated.
A: No damage at 20 mm B: No damage at 25 mm, damage at 20 mm C: Damage at 25 mm

[result]
Table 1 is shown below.
In addition, when two or more kinds of the same kind of components are described together with the value of the ratio in one mass, it indicates that those the same kind of components are used in the described ratio (mass ratio). For example, Example 77 contains the epoxy compound B-3 / B-9 in a 50/50 (mass ratio).

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.

Further, as the phenol compound, when the phenol compound having my of 1 in the general formula (Y) is used as the phenol compound satisfying the requirement 1, or when the phenol compound satisfying the requirement 2 is used, the obtained heat conductive material It was confirmed that the thermal conductivity and / or peel strength was better (see comparison of the results of the examples using B-2 as the epoxy compound, etc.).

When an epoxy compound exhibiting liquid liquidity or an epoxy compound represented by the general formula (DN) is used as the epoxy compound, it has been confirmed that the obtained heat conductive material has more excellent heat conductivity and / or peel strength. (See the results of examples in which B-4, B-6, B-7, or B-8 is used as the epoxy compound).

When a bisphenol F type epoxy compound, an epoxy compound represented by the general formula (E1), or an epoxy compound having a diglycidylamino group is used as the epoxy compound having a flexible structure or excellent moldability, the composition is used. It was confirmed that the semi-cured sheet formed had better storage stability (results of Examples using B-3, B-10, B-13, B-14, or B-15 as the epoxy compound). Etc.).

It was confirmed that when the epoxy compound has an aromatic ring group, the thermal conductivity of the heat conductive material is more excellent (comparing the examples using A-3 as the phenol compound, the epoxy compound having an aromatic ring group is used. When used, thermal conductivity is rated A).

When a bisphenol F type epoxy compound and a phenoxy resin are used, when a bisphenol F type epoxy compound and a phenol novolac type epoxy compound are used, and when a polyhydroxybenzene type epoxy compound and a phenol novolac type epoxy compound are used. It was confirmed that the effects of the present invention can be realized in a more balanced manner (see the results of Examples 77 to 80, etc.).

It was confirmed that when a compound represented by the general formula (Z2) was used as the phenol compound, the storage stability of the semi-cured sheet formed from the composition was better, and the results such as thermal conductivity were also better. (See the results of examples using A-8 or A-9 as the phenolic compound, etc.).
This is because the phenol compound satisfying the requirement 2 is "an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group" and another "aromatic ring group having a phenolic hydroxyl group". It is considered that by having both of the above, the symmetry of the compound is broken and the melting point is lowered, and as a result, the flexibility at the time of semi-curing is introduced while maintaining the good thermal conductivity at the time of curing.

It was confirmed that when the content of the curing accelerator was 0.07% by mass or more with respect to the total solid content of the composition, the heat conductivity and / or withstand voltage of the obtained heat conductive material was more excellent ( See comparison of results of Examples 97 and 103, etc.). It is considered that this is because the reaction rate of the curing reaction was improved due to the sufficient content of the curing accelerator.
It was confirmed that the effect of the present invention was more excellent when the content of the curing accelerator was 2% by mass or less based on the total solid content of the composition (see comparison of the results of Examples 111 and 112, etc.). ). It is considered that this is because the content of the curing accelerator is not more than a certain amount, so that the curing accelerator itself can be prevented from becoming a factor that impairs various performances of the heat conductive material as an impurity.

Claims

A curable composition comprising a phenol compound, an epoxy compound, a curing accelerator, and an inorganic substance.
The phenolic compound satisfies at least one of Requirement 1 and Requirement 2.
A curable composition in which the content of the inorganic substance is more than 10% by mass with respect to the total solid content.
Requirement 1: A compound represented by the general formula (Y).
Requirement 2: A phenol compound having a triazine skeleton and having an aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group.

In the general formula (Y), my represents an integer of 0 or more.
RY1 and RY2 each independently represent an aromatic ring group having a phenolic hydroxyl group and a substituent having 1 to 6 carbon atoms arranged at the ortho position of the phenolic hydroxyl group.
LY1 and LY2 independently represent -C ( RY5 ) ( RY6)-or- CO-, respectively.
RY3 to RY6 independently represent a hydrogen atom or a substituent.
The curable composition according to claim 1, wherein the temperature at which the exothermic peak is detected is 140 ° C. or higher when the semi-curable sheet formed by using the curable composition is measured by a differential scanning calorimeter. ..
The curable composition according to claim 1 or 2, wherein the epoxy compound has a molecular weight of 300 or more.
The curable composition according to any one of claims 1 to 3, wherein the inorganic substance contains aggregated boron nitride having an average particle size of 20 μm or more.
The curable composition according to any one of claims 1 to 4, wherein the phenol compound contains a compound represented by the general formula (Z).

In the general formula (Z), r represents an integer of 0 or more.
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.
L represents a divalent organic group.
E 1 to E 6 independently represent a single bond, -NH-, or -NR-. R represents a substituent.
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.
X 1 to X 4 each independently represent an aromatic ring group having a phenolic hydroxyl group.
However, at least one of k X 1 , l X 2 , r × m X 3 , and n X 4 is a phenolic hydroxyl group and the phenolic hydroxyl group. Represents an aromatic ring group having a substituent arranged at the ortho position.
The curable composition according to any one of claims 1 to 5, wherein the phenol compound contains a compound represented by the general formula (Z1).

In the general formula (Z1), r represents an integer of 0 or more.
L represents a divalent organic group.
R Z represents a hydrogen atom or a substituent.
Provided that at least one of R Z which in the general formula (Z1) (3 + r) pieces there is a substituent.
Further, at least one of R Z which in the general formula (Z1) (3 + r) pieces there is a hydrogen atom.
The curable composition according to any one of claims 1 to 6, wherein the phenol compound contains a compound represented by the general formula (Z2).

In the general formula (Z2), R Z represents a hydrogen atom or a substituent.
Provided that at least one of the two existing R Z in the general formula (Z2) represents a substituent.
The curable composition according to any one of claims 1 to 7, wherein the curing accelerator contains a compound containing a phosphorus atom.
The curable composition according to any one of claims 1 to 8, wherein the curing accelerator contains a phosphonium salt.
A heat conductive material obtained by curing the curable composition according to any one of claims 1 to 9.
A heat conductive sheet made of the heat conductive material according to claim 10.
A device with a heat conductive layer having a device and a heat conductive layer including the heat conductive sheet according to claim 11 arranged on the device.
A compound represented by the general formula (Z).

In the general formula (Z), r represents an integer of 0 or more.
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.
L represents a divalent organic group.
E 1 to E 6 independently represent a single bond, -NH-, or -NR-. R represents a substituent.
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.
X 1 to X 4 each independently represent an aromatic ring group having a phenolic hydroxyl group.
However, at least one of k X 1 , l X 2 , r × m X 3 , and n X 4 is a phenolic hydroxyl group and the phenolic hydroxyl group. Represents an aromatic ring group having a substituent arranged at the ortho position.
The compound according to claim 13, which is represented by the general formula (Z1).

In the general formula (Z1), r represents an integer of 0 or more.
L represents a divalent organic group.
R Z represents a hydrogen atom or a substituent.
Provided that at least one of R Z which in the general formula (Z1) (3 + r) pieces there is a substituent.
Further, at least one of R Z which in the general formula (Z1) (3 + r) pieces there is a hydrogen atom.
The compound according to claim 13 or 14, represented by the general formula (Z2).

In the general formula (Z2), R Z represents a hydrogen atom or a substituent.
Provided that at least one of the two existing R Z in the general formula (Z2) represents a substituent.