JP2019116595A - Heat conduction material forming composition, heat conduction material, and device with heat conduction layer - Google Patents

Abstract

To provide a heat conduction material forming composition having excellent heat conductivity, a heat conduction material, and a device with a heat conduction layer.SOLUTION: A heat conduction material forming composition has a charge transfer complex, the charge transfer complex at least containing a disk-shaped compound. Alternatively, in the heat conduction material forming composition, the charge transfer complex may contain a disk-shaped compound and a compound having a redox potential to a saturated calomel electrode of 0 V or more.SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming a heat transfer material, a heat transfer material, and a device with a heat transfer layer.

Power semiconductor devices used in various electrical devices such as personal computers, general home appliances, and automobiles have been rapidly miniaturized in recent years. With the miniaturization, control of heat generated from a high density power semiconductor device has become difficult.
In order to cope with such a problem, a thermally conductive material is used which promotes heat dissipation from the power semiconductor device.
For example, Patent Document 1 discloses an epoxy resin composition for a heat conductive material containing an epoxy resin having a triphenylene skeleton, a curing agent or a curing accelerator, and an inorganic filler, and a thermally conductive material obtained by curing the above composition. ing.

JP, 2017-008153, A

  When the present inventors examined the heat conduction material described in patent document 1, it became clear that heat conductivity did not satisfy | fill the level currently calculated | required now, and the further improvement is required.

Then, this invention makes it a subject to provide the composition for heat conductive material formation which can give the heat conductive material which is excellent in heat conductivity.
Another object of the present invention is to provide a thermally conductive material formed by the composition for forming a thermally conductive material, and a device with a thermally conductive layer.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by using the charge transfer complex containing a discotic compound as a result of earnestly examining in order to achieve the said subject, and completed this invention.
That is, it discovered that the said objective could be achieved by the following structures.

[1] containing a charge transfer complex,
The composition for heat conductive material formation in which the said charge transfer complex contains a discotic compound at least.
[2] The composition for forming a heat conducting material according to [1], wherein the charge transfer complex is composed of the discotic compound and a compound having an oxidation reduction potential of 0 V or more with respect to a saturated calomel electrode.
[3] The composition for forming a heat transfer material according to [2], wherein the charge transfer complex is composed of the discotic compound and a compound having an oxidation reduction potential to the saturated calomel electrode of 0 V or more and 0.50 V or less.
[4] The heat according to [2] or [3], wherein the discotic compound is selected from the group consisting of a compound represented by Formula (D4) described later and a compound represented by Formula (D16) described later Composition for conductive material formation.
[5] The composition for forming a heat conductive material according to any one of [2] to [4], wherein the discotic compound contains a polymerizable group.
[6] The composition for forming a heat conductive material according to [1], wherein the charge transfer complex is composed of two or more discotic compounds having different structures.
[7] The composition for forming a heat conductive material according to [6], wherein at least one of the discotic compounds contains a polymerizable group.
[8] The composition for forming a heat conductive material according to [7], wherein one of the discotic compounds contains a polymerizable group and the other contains a crosslinkable group.
[9] The charge transfer complex is selected from the group consisting of a discotic compound containing a partial structure represented by Formula (CR1) described later and a discotic compound containing a partial structure represented by Formula (CR2) described later And two or more discotic compounds, and
The composition for forming a heat conductive material according to any one of [6] to [8], wherein the partial structures of the two or more kinds of discotic compounds are different from each other.
[10] A discotic compound including the partial structure represented by the above formula (CR1) in which the charge transfer complex represents any one of the above-mentioned X ^CR11 to the above X ^CR16 , and the above X ^CR11 to the above X ^CR16 The composition for heat conductive material formation as described in [9] which consists of a discotic compound which contains the partial structure represented by said Formula (CR1) which represents -C (= O)-in any case.
[11] The composition for forming a heat conductive material according to any one of [1] to [10], further containing an inorganic substance.
[12] A thermally conductive material formed using the composition for forming a thermally conductive material according to any one of [1] to [11].
[13] The thermally conductive material according to [12], which is in the form of a sheet.
[14] A device with a thermally conductive layer, comprising: a device; and a thermally conductive layer containing the thermally conductive material according to [12] or [13] disposed on the device.

ADVANTAGE OF THE INVENTION According to this invention, the composition for heat conductive material formation which can provide the heat conductive material which is excellent in heat conductivity can be provided.
Further, according to the present invention, it is possible to provide a thermally conductive material formed by the composition for forming a thermally conductive material and a device with a thermally conductive layer.

Hereinafter, the composition for heat conductive material formation of the present invention, a heat conductive material, and a device with a heat conductive layer are explained in detail.
The description of the configuration requirements described below may be made based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the present specification, an oxiranyl group is a functional group also referred to as an epoxy group, and for example, a group in which two adjacent carbon atoms of a saturated hydrocarbon ring group are linked via an oxo group (-O-) to form an oxirane ring. Etc. are also included in the oxiranyl group.

In the present specification, the description of "(meth) acryloyl group" represents the meaning of "any one or both of an acryloyl group and a methacryloyl group".
In the present specification, the description “(meth) acrylamide group” means the meaning of “one or both of an acrylamide group and a methacrylamide group”.

  In addition, in this specification, the kind of substituent in the case of "it may have a substituent", the position of a substituent, and the number of substituents are not specifically limited. The number of substituents is, for example, one or two or more. Examples of the substituent include monovalent nonmetal atomic groups other than hydrogen atoms, and can be selected, for example, from the following substituent group Y.

Substituent group Y:
Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, amino group, carboxy group and its conjugate base group, carboxylic acid anhydride group, cyanate ester group, unsaturated polymerizable group, oxiranyl group, oxetanyl group, Aziridinyl group, thiol group, isocyanate group, thioisocyanate group, aldehyde group, alkoxy group, aryloxy 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-dialkyl Carbamoyloxy group, N, N-diaryl car Moyloxy, N-alkyl-N-arylcarbamoyloxy, alkylsulfoxy, arylsulfoxy, acylthio, acylamino, N-alkylacylamino, N-arylacylamino, ureido, N'- Alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N -Aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl ureido group, N ', N'-dialkyl-N-alkyl ureido group, N', N'-dialkyl-N -Aryl ureido group, N'-aryl-N-alkyl ureido group, N'-aryl-N-aryl ureido group, N ', N'-dia -N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N -Aryl ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl- N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N- Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N -Alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acyl Sulfamoyl group and its conjugated base group, N-aryl Le acylsulfamoyl group _{(-SO 2 NHSO 2 (alkyl)} ) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonyl Carbamoyl group (-CONHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonyl carbamoyl group (-CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (-Si (Oalkyl) ₃ ), aryloxy Silyl group (-Si (Oaryl) ₃ ), hydroxysilyl group (-Si (OH) ₃ ) and its conjugate base group, phosphono group (-PO ₃ H ₂ ) and its conjugate base group, dialkyl phosphono group (-PO) ₃ (alkyl) _2), diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkylaryl Ruhosuhono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group, monoaryl phosphono group (-PO ₃ H (aryl)) and its Conjugated base group, phosphonooxy group (-OPO ₃ H ₂ ) and conjugated base group thereof, dialkyl phosphonoxy group (-OPO ₃ (alkyl) ₂ ), diarylphosphonoxy group (-OPO ₃ (aryl) ₂ ), alkyl aryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-OPO ₃ H (alkyl)) and its conjugated base group, monoarylphosphono group (-OPO ₃ H ( aryl) and its conjugated base group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group, and alkyl group.
In addition, if possible, these substituents may be combined with each other or with a substituted group to form a ring.

  In addition, as an unsaturated polymerizable group, the substituent etc. which are represented by (meth) acryloyl group, a (meth) acrylamide group, and Q1-Q7 shown below are mentioned, for example.

[Composition for forming heat conductive material]
The feature of the composition for forming a heat conductive material of the present invention (hereinafter, also referred to as “the composition of the present invention”) includes a point including a charge transfer complex containing at least a discotic compound.
As used herein, the term "charge transfer complex" refers to an intermolecular compound consisting of an electron donating molecule (electron donor) and an electron accepting molecule (electron acceptor) and having charge transfer interaction. .
The charge transfer theory by molecular orbital theory is described by R. S. The charge transfer amount of complex D ·· A, which is defined by Mulliken and is formed from an electron donor D (electron donor) and an electron acceptor A (electron acceptor), is represented by δ, the following equation holds, A new absorption band (charge transfer absorption band) which does not appear in the body or the electron acceptor alone appears in the long wavelength side. Also, as the electron affinity of the electron acceptor increases, the wavelength of the absorption maximum shifts to the long wavelength side.

The charge transfer complex used in the present invention contains at least a discotic compound (eg, triphenylene derivative etc.). In other words, at least one of the electron donor and the electron acceptor that forms the charge transfer complex is a discotic compound.
Both the electron donor and the electron acceptor are neutral compounds which are not ionized or partially ionized before forming a complex, and they are mixed to achieve charge transfer only when they approach molecules. It forms to form a complex.

According to the above configuration, the thermally conductive material formed by the composition of the present invention is excellent in thermal conductivity.
The reason for this is not clear in detail, but in the heat conductive material formed from the composition for forming a heat conductive material, the discotic compound in the charge transfer complex has either an alternate layer orientation or an alternate layer orientation. It is assumed that the highly ordered state of orientation is formed by taking the, and as a result, the thermal conductivity is excellent.
The inventors of the present invention have studied that, when a discotic liquid crystal compound is aligned to form a columnar phase, the range over which the alignment control force of the liquid crystal compound extends is about 5 μm, as described above. In the case where the discotic compound is oriented in the form of a charge transfer complex, it is presumed that a highly ordered orientation can be achieved with a thicker film thickness. That is, by orienting the discotic compound in the form of charge transfer complex, the discotic compound is oriented with a high degree of order even in a thermally conductive member having a large film thickness (generally about 100 μm) such as a thermally conductive sheet. As a result, it is considered that excellent thermal conductivity is developed.
In addition, the discotic compound can arrange a plurality of side chains each including a reactive group (preferably, a polymerizable group) radially to the central nucleus (that is, it is a structure that easily expands the heat conduction path). It is thought that it contributes to the improvement of the thermal conductivity.
In addition, it is preferable that the discotic compound in a charge transfer complex is a discotic liquid crystalline compound at the point which the heat conductivity of a heat conductive material is more excellent. Moreover, for the same reason, the composition of the present invention preferably exhibits liquid crystallinity. When the discotic compound in the charge transfer complex exhibits liquid crystallinity, the composition generally exhibits liquid crystallinity as well.

  Hereinafter, the components contained in the composition for forming a heat transfer material will be described in detail, and then, the method for producing the composition for forming a heat transfer material, the use thereof and the like will be described in detail.

<Charge transfer complex>
In the charge transfer complex contained in the above composition, at least one of the electron donor and the electron acceptor forming the charge transfer complex is a discotic compound.

Among the charge transfer complexes, the electron donor and the electron acceptor are preferably both organic substances. That is, in the charge transfer complex, it is preferable that the molecule forming the charge transfer complex with the discotic compound is also an organic substance.
The embodiment of the charge transfer complex containing a discotic compound is not particularly limited, but examples of the specific embodiment include the charge transfer complexes of the embodiments (1) and (2) described below.
Aspect (1): Charge transfer complex wherein the electron donor and the electron acceptor are discotic compounds having mutually different structures (2): The electron donor is a discotic compound, and the electron acceptor is a redox compound to a saturated calomel electrode Charge transfer complex which is a compound having a potential of 0 V or more

In the composition, only one type of charge transfer complex may be used, or two or more types may be used in combination.
Although the content of the charge transfer complex in the composition is not particularly limited, it is, for example, 0.01 to 99.9% by mass, preferably 0.01 to 80% by mass, with respect to the total solid content of the composition. 0.1-65 mass% is more preferable, and 1-50 mass% is further more preferable. In addition, in this specification, solid content should just be a component which comprises a heat conductive material, and even if it is liquid, it is contained in solid content.

Below, the discotic compound which a charge transfer complex may contain is demonstrated first.
(Disc-like compounds)
By "disc-like compound" herein is intended a compound that at least partially comprises a disc-like structure.
As the discotic compound, a compound having at least an aromatic ring and capable of forming a stacking structure based on π-π interaction between molecules to form a columnar structure is preferable.
In addition, the discotic compound preferably contains 3 to 8 reactive groups (preferably, a polymerizable group) in that the heat conduction path is extended, and as a result, the heat conductivity of the heat conduction material is more excellent. It is more preferable to include six. The cured product of the discotic compound having three or more reactive groups has a high glass transition temperature and exhibits excellent heat resistance.
In addition, with a reactive group, a polymeric group and a crosslinkable group are intended, and among these, a polymeric group is preferable.
The type of the polymerizable group is not particularly limited, and may be a known polymerizable group. From the viewpoint of reactivity, a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferred. More preferable. Examples of the polymerizable group include a (meth) acryloyl group, a vinyl group, an oxiranyl group, and an oxetanyl group, among which a (meth) acryloyl group, a vinyl group or an oxiranyl group is preferable from the viewpoint of reactivity. preferable. In addition, the hydrogen atom in each said group may be substituted by other substituents, such as a halogen atom.
Moreover, as a crosslinkable group, a hydroxyl group, a carboxy group, a carboxylic acid anhydride group, an amino group, a halogen atom, an isocyanate group, a cyano group, an aziridinyl group, a thiol group, a thioisocyanate group, an aldehyde group etc. are mentioned, for example.

  The discotic compound may be a liquid crystal compound exhibiting liquid crystallinity or a non-liquid crystal compound not exhibiting liquid crystallinity, but a liquid crystal compound is preferable in that the thermal conductivity of the heat conductive material is more excellent. That is, as a discotic compound, a discotic liquid crystal compound is preferable.

  Specific examples of the discotic compound include C.I. Destrade et al. , Mol. Crysr. Liq. Cryst. , Vol. 71, page 111 (1981); The Chemical Society of Japan, Ed. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10, Section 2 (1994); Kohne et al. , Angew. Chem. Soc. Chem. Comm. , Page 1794 (1985); Zhang et al. , J. Am. Chem. Soc. , Vol. 116, page 2655 (1994), and compounds described in patent 4592225. As discotic compounds, Angew. Chem. Int. Ed. 2012, 51, 7990-7993 and the triphenylene structure described in JP-A-7-306317, and the trisubstituted benzene structure described in JP-A 2007-2220 and JP-A 2010-244038 .

As the discotic compound, a compound represented by any one of the formulas (D1) to (D17) shown below is preferable in that the heat conductivity of the heat conductive material is more excellent, and (D1) to (D16) are more preferable. preferable.
In the following formulas, "-LQ" represents "-L-Q" and "QL-" represents "Q-L-".

In formulas (D1) to (D15), L represents a divalent linking group.
L independently represents an alkylene group, an alkenylene group, an arylene group, -C (= O)-, -NH-, -O-, -S-, and-in that the thermal conductivity of the thermally conductive material is more excellent. It is preferably a group selected from the group consisting of these combinations, and is selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -C (= O)-, -NH-, -O-, and -S- It is more preferable that it is the group which combined two or more groups.
As a carbon number of the said alkylene group, 1-12 are preferable. As a carbon number of the said alkenylene group, 2-12 are preferable. As carbon number of the said arylene group, 10 or less is preferable. In addition, the said alkylene group, the said alkenylene group, and the said arylene group may have a substituent further. The substituent is not particularly limited, and examples thereof include an alkyl group, a halogen atom, cyano, an alkoxy group, and an acyloxy group.

An example of L is shown below. In the following example, the bond on the left side is bonded to the central nucleus (hereinafter, also simply referred to as "central ring") of the compound represented by any one of formulas (D1) to (D15), and the bond on the right side is Q Bond to
AL means an alkylene group or an alkenylene group, and AR means an arylene group.

L101: -AL-C (= O) -O-AL-
L102: -AL-C (= O) -O-AL-O-
L103: -AL-C (= O) -O-AL-O-AL-
L104: -C (= O) -AR-O-AL-
L105: -C (= O) -AR-O-AL-O-
L106: -C (= O) -NH-AL-
L107: -NH-AL-O-
L108: -O-AL-
L109: -O-AL-O-

L110: -O-AL-OC (= O) -NH-AL-
L111: -O-AL-S-AL-
L112: -O-C (= O) -AL-AR-O-AL-
L113: -O-C (= O) -AL-AR-O-AL-O-
L114: -O-C (= O) -AR-O-AL-C (= O)-
L115: -O-C (= O) -AR-O-AL-
L116: -O-C (= O) -AR-O-AL-O-
L117: -O-C (= O) -AR-O-AL-O-AL-
L118: -O-C (= O) -AR-O-AL-O-AL-O-
L119: -O-C (= O) -AR-O-AL-O-AL-O-AL-
L120: -O-C (= O) -AR-O-AL-O-AL-O-AL-O-
L121: -S-AL-
L122: -S-AL-O-
L123: -S-AL-S-AL-
L124: -S-AR-AL-
L125: -O-C (= O) -AL-
L126: -O-C (= O) -AL-O-
L127: -O-C (= O) -AR-O-AL-
L128: -O-C (= O) -AR-O-AL-O-C (= O) -AL-S-AR-
L129: -O-C (= O) -AL-S-AR-
L130: -O-C (= O) -AR-O-AL-O-C (= O) -AL-S-AL-
L131: -O-C (= O) -AL-S-AR-
L132: -O-AL-S-AR-
L133: -AL-C (= O) -O-AL-OC (= O) -AL-S-AR-
L134: -AL-C (= O) -O-AL-OC (= O) -AL-S-AL-
L135: -O-AL-O-AR-
L136: -O-AL-OC (= O) -AR-
L137: -O-AL-NH-AR-
L138: -O-C (= O) -AL-O-AR-
L139: -O-C (= O) -AR-O-AL-O-AR-
L140: -AL-C (= O) -O-AR-
L141: -AL-C (= O) -O-AL-O-AR-
L142: -O-AL-O-AL-

In formulas (D1) to (D15), Q each independently represents a hydrogen atom or a substituent.
Examples of the substituent include the groups exemplified in the above-mentioned Substituent Group Y. Among them, a reactive group is preferable, and an unsaturated polymerizable group, an oxiranyl group, an oxetanyl group, a hydroxyl group, a carboxy group, a carboxylic acid anhydride Groups, amino groups, halogen atoms, isocyanate groups, cyano groups, aziridinyl groups, thiol groups, thioisocyanate groups, or aldehyde groups are more preferred.
In formulas (D1) to (D15), at least one Q is preferably a reactive group, and in particular, all Qs represent a reactive group in that the thermal conductivity of the heat conductive material is more excellent. Is preferred. The reactive group is preferably a polymerizable group, more preferably a (meth) acryloyl group, a vinyl group, an oxiranyl group or an oxetanyl group, and still more preferably a (meth) acryloyl group, a vinyl group or an oxiranyl group.

Among the compounds represented by the formulas (D1) to (D15), the compound represented by the formula (D4) is preferable in that the thermal conductivity of the heat conductive material is more excellent. In other words, the central ring of the discotic compound is preferably a triphenylene ring.
As a compound represented by Formula (D4), the compound represented by Formula (XI) is preferable at the point which the heat conductivity of a heat conductive material is more excellent.

Wherein ^{(XI), R 11, R} 12, R 13, R 14, R 15 and R ^16, each ^{independently, * - X 11 -L 11 -P} 11, or * -X ¹² -L ¹² - representing the Y ^12.
In addition, * represents a bonding position with a triphenylene ring.
^{R 11, R 12, R 13} , R 14, R 15, and of the R ^16, two or more may, * - X ¹¹ is -L ¹¹ -P ^11, 3 or more is * -X ¹¹ -L ¹¹ it is preferable that the -P ^11.
Among them, any one or more of R ¹¹ and R ¹² , any one or more of R ¹³ and R ¹⁴ , and any one of R ¹⁵ and R ¹⁶ in that the thermal conductivity of the heat conductive material is more excellent. or one is * - is preferably X ¹¹ -L ¹¹ -P ^11.
More preferably, all of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are * -X ¹¹ -L ¹¹ -P ¹¹ . In addition, it is further preferred that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all identical.

Each X ¹¹ independently represents a single bond, -O-, -C (= O)-, -NH-, -OC (= O)-, -OC (= O) O-, -OC (= O) NH-, -OC (= O) S-, -C (= O) O-, -C (= O) NH-, -C (= O) S-, -NHC (= O)-, -NHC ( OO—, —NHC (= O) NH—, —NHC (= O) S—, —S—, —SC (= O) —, —SC (= O) O—, —SC (= O) And n represents an —NH— or —SC (= O) S—.
Among them, each X ¹¹ independently represents —O—, —OC (= O) —, —OC (= O) O—, —OC (= O) NH—, —C (= O) O—, -C (= O) NH-, -NHC (= O)-, or -NHC (= O) O- is preferable, and -O-, -OC (= O)-, -C (= O) O-, -OC (= O) NH- or -C (= O) NH- is more preferable, and -C (= O) O- is more preferable.

Each L ¹¹ independently represents a single bond or a divalent linking group.
Examples of the divalent linking group include -O-, -OC (= O)-, -C (= O) O-, -S-, -NH-, and an alkylene group (having 1 to 10 carbon atoms). Preferably, 1 to 8 are more preferable, and 1 to 7 are further preferable), an arylene group (having 6 to 20 carbon atoms, more preferably 6 to 14 and still more preferably 6 to 10 carbon atoms), or such The group which consists of a combination is 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 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, and anthracenylene 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, and more preferably 1. The substitution position of the substituent is not particularly limited. As a substituent, a halogen atom or a C1-C3 alkyl group is preferable, and a methyl group is more preferable.
It is also preferable that the said alkylene group and the said arylene group are unsubstituted. Among them, the alkylene group is preferably unsubstituted.

Examples of -X ¹¹ -L ^11- include L101 to L142 which are the examples of L described above.

P ¹¹ represents a reactive group. The definition of the reactive group is as described above.
Among them, as P ¹¹ , a (meth) acryloyl group, a vinyl group or an oxiranyl group is preferable from the viewpoint of reactivity. In addition, the hydrogen atom in each said group may be substituted by other substituents, such as a halogen atom.
When P ¹¹ is a hydroxyl group, L ¹¹ preferably includes an arylene group, and the arylene group is preferably bonded to P ¹¹ .

X ¹² is the same as X ¹¹ , and preferred conditions are also the same.
L ¹² is the same as L ¹¹ , and preferred conditions are also the same.
-X ¹² -L ¹² - Examples of include L101~L142 examples of the above-mentioned L.

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; pieces or two or more methylene groups are -O -, - S -, - NH -, - N (CH 3) -, - C (= O) -, - OC (= O) -, or -C (= O) represents a group substituted with O-.

Y ¹² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or 1 or 2 in a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms Or more methylene groups are —O—, —S—, —NH—, —N (CH ₃ ) —, —C (= O) —, —OC (= O) —, or —C (= O) O In the case of a group substituted with-, one or more of the hydrogen atoms contained in Y ¹² may be substituted with a halogen atom.
Y ¹² is preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an alkylene oxide group having 1 to 20 carbon atoms, and the linear or 1 to 12 carbon atoms A branched alkyl group or an ethylene oxide or propylene oxide group having 1 to 20 carbon atoms is more preferable.

  About the specific example of a compound represented by Formula (XI), Paragraph No. 0028 of Unexamined-Japanese-Patent No. 7-281028, Unexamined-Japanese-Patent No. 7-306317, Paragraph No. 0016-00182 of Unexamined-Japanese-Patent No. 2005-156822. JP-A-2006-301614, Paragraph Nos. 0067 to 0072, and the liquid crystal handbook (published by Maruzen 2000), pages 330 to 333 can be referred to.

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

  Moreover, the compound represented by Formula (D16) as a discotic compound is also preferable at the point which the heat conductivity of a heat conductive material is more excellent.

In formula (D16), ^A2X , ^A3X , and ^A4X respectively independently represent -CH = or -N =. Among them, A ^2X , A ^3X and A ^4X are preferably each independently —CH =.
R ^17X, R ^18X, and R ^19X are independently * - represents the _{^{(X 211X -Z 21X) n21X -L}} 21X -Q. * Represents the bonding position with the central ring.
X ²¹¹ X is each independently a single bond, -O-, -C (= O)-, -NH-, -OC (= O)-, -OC (= O) O-, -OC (= O) NH-, -OC (= O) S-, -C (= O) O-, -C (= O) NH-, -C (= O) S-, -NHC (= O)-, -NHC ( OO—, —NHC (= O) NH—, —NHC (= O) S—, —S—, —SC (= O) —, —SC (= O) O—, —SC (= O) And n represents an —NH— or —SC (= O) S—.
Z ^21X each independently represents a 5- or 6-membered aromatic ring group, or a 5- or 6-membered non-aromatic ring group.
L ^{21 X} represents a single bond or a divalent linking group.
Q is synonymous with Q in Formula (D1)-(D15), and its preferable aspect is also the same.
n21X represents an integer of 0 to 3; If n21X is 2 or more, there are a plurality (X ^211X -Z ^21X) may be the same or different.

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

In formula (XII), A ² , A ³ and A ⁴ each independently represent -CH = or -N =. Among them, A ² , A ³ and A ⁴ are preferably —CH =. In other words, it is also preferable that the central ring of the discotic compound is a benzene ring.

Each of R ¹⁷ , R ¹⁸ and R ¹⁹ independently represents *-(X ²¹¹ -Z ²¹ ) _n ²¹ -L ²¹ -P ²¹ or *-(X ²²¹ -Z ²² ) _n ²² -Y ²² . * Represents the bonding position with the central ring.
Two or more of R ¹⁷ , R ¹⁸ and R ¹⁹ are *-(X ²¹¹ -Z ²¹ ) _n ²¹ -L ²¹ -P ²¹ . It is preferable that all of R ¹⁷ , R ¹⁸ , and R ¹⁹ be *-(X ²¹¹ -Z ²¹ ) _n ²¹ -L ²¹ -P ²¹ in that the heat conductivity of the heat conductive material is more excellent.
In addition, it is preferred that R ¹⁷ , R ¹⁸ and R ¹⁹ are all identical.

Each of X ²¹¹ and X ²²¹ independently represents a single bond, -O-, -C (= O)-, -NH-, -OC (= O)-, -OC (= O) O-, -OC ( = O) NH-, -OC (= O) S-, -C (= O) O-, -C (= O) NH-, -C (= O) S-, -NHC (= O)-, -NHC (= O) O-, -NHC (= O) NH-, -NHC (= O) S-, -S-, -SC (= O)-, -SC (= O) O-, -SC (= O) NH- or -SC (= O) S-.
Among them, each of X ²¹¹ and X ²²¹ is preferably independently a single bond, -O-, -C (= O) O-, or -OC (= O)-.

Z ²¹ and Z ²² each independently represent a 5- or 6-membered aromatic ring group, or a 5- or 6-membered non-aromatic ring group, for example, a 1,4-phenylene group, There may be mentioned 1,3-phenylene and aromatic heterocyclic groups.

  The aromatic ring group and the non-aromatic ring group may have a substituent. The number of substituents is preferably 1 or 2, and more preferably 1. The substitution position of the substituent is not particularly limited. As a substituent, a halogen atom or a methyl group is preferable. It is also preferable that the said aromatic ring group and the said non-aromatic ring group are unsubstituted.

As an aromatic heterocyclic group, the following aromatic heterocyclic groups are mentioned, for example.

In formula, * represents the site ^| part which couple ^| bonds with ^X211 or ^X221 . ** represents a site that binds to X ²¹² or X ²²² . Each of A ⁴¹ and A ⁴² independently represents a methine group or a nitrogen atom. X ⁴ represents an oxygen atom, a sulfur atom, a methylene group or an imino group.
At least one of A ⁴¹ and A ⁴² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. In addition, X ⁴ is preferably an oxygen atom.

For described below n21 and n22 is 2 or more, there are a plurality (X ²¹¹ -Z ²¹⁾ and (X ²²¹ -Z ²²⁾ may each be the same or different.

L ²¹ each independently represents a single bond or a divalent linking group, and has the same meaning as L ¹¹ in formula (XI) described above. L ²¹ is —O—, —OC (= O) —, —C (= O) O—, —S—, —NH— or an alkylene group (the number of carbon atoms is preferably 1 to 10, 1 to 8) Is more preferable, 1 to 7 is further preferable), an arylene group (having 6 to 20 carbon atoms, more preferably 6 to 14 and still more preferably 6 to 10 carbon atoms), or a group consisting of a combination thereof preferable.

When n22 to be described later is 1 or more, examples of -L ^21- include L101 to L142 which are examples of L in the above formulas (D1) to (D15).

P ²¹ represents a reactive group. The definition of the reactive group is as described above.
Among them, as P ²¹ , a (meth) acryloyl group, a vinyl group or an oxiranyl group is preferable from the viewpoint of reactivity. In addition, the hydrogen atom in each said group may be substituted by other substituents, such as a halogen atom.
When P ²¹ is a hydroxyl group, L ²¹ preferably includes an arylene group, and the arylene group is preferably bonded to P ²¹ .

Y ²² 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; pieces or two or more methylene groups are -O -, - S -, - NH -, - N (CH 3) -, - C (= O) -, - OC (= O) -, or -C (= O) represents a group substituted with O-. Preferred embodiments of Y ²² are the same as the preferred embodiments of Y ¹² in formula (XI).

  n21 and n22 each independently represent an integer of 0 to 3, and from the viewpoint of more excellent thermal conductivity, the integer of 1 to 3 is preferable, and 2 to 3 is more preferable.

Preferred examples of the compound represented by the formula (XII) include the following compounds.
Incidentally, in the following structural formulas, R represents an -X ²¹¹ -L ²¹ -P ^21.

  The details of the compound represented by the formula (XII) and specific examples can be referred to the description of paragraphs 0013 to 0077 of JP-A-2010-244038, the contents of which are incorporated herein.

  The compounds 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 discotic compound is preferably a compound having a hydrogen bonding functional group from the viewpoint of strengthening the stacking by reducing the electron density and facilitating formation of a column-like assembly. As a hydrogen bonding functional group, -OC (= O) NH-, -C (= O) NH-, -NHC (= O)-, -NHC (= O) O-, -NHC (= O) NH -, -NHC (= O) S-, or -SC (= O) NH- and the like.

  Moreover, the compound represented by Formula (D17) can also be used as a discotic compound for forming the charge transfer complex of this invention.

  In said Formula (D17), L and Q are respectively synonymous with L and Q in Formula (D1)-(D15), and a preferable aspect is also the same.

(Charge transfer complex of aspect (1))
In the charge transfer complex of the above-described aspect (1), both the electron donor and the electron acceptor are discotic compounds. That is, the charge transfer complex which consists of 2 or more types of discotic compounds from which a structure mutually differs corresponds. The discotic compound is as described above.
In the charge transfer complex, which one of the electron donor and the electron acceptor the two or more kinds of discotic compounds having different structures show is referred to as an atom or atomic group near the central ring (hereinafter, “atomic group etc.”). It is relatively determined depending on the type of) and the structure of the central ring. That is, for example, a charge transfer complex consisting of two or more kinds of compounds represented by the above-mentioned formula (D4) different in structure from each other, and an atomic group bonded to the central ring in L bonded to the central ring (triphenylene ring) Charge transfer comprising a discotic compound of the type such as -O- and a discotic compound of the type such as an atomic group binding to the central ring in L bonded to the central ring In the complex, the discotic compound in which the type of the above atomic group and the like is -O- functions as an electron donor, and the discotic compound in which the type of the above atomic group and the like is -C (= O)-is an electron It functions as a receptor.

  Above all, as the charge transfer complex of the above aspect (1), a discotic compound including a partial structure represented by the following formula (CR1), and a compound represented by the following formula (CR2) Preferred is a charge transfer complex selected from the group consisting of discotic compounds containing a partial structure represented by the above, and formed from two or more discotic compounds having different partial structures from each other.

In the formula, each of X ^{CR11 to} X ^CR16 independently represents a single bond, -O-, -C (= O)-, -NH-, or -S-. * Represents a bonding position.

  Specifically, among the compounds represented by the above-mentioned formula (D4), the partial structure represented by the above-mentioned formula (CR1) is exemplified as the compound including the partial structure represented by the above-mentioned formula (CR1) Include.

In the formulae, X ^CR21 , X ^CR22 and X ^CR23 each independently represent a single bond, -O-, -C (= O)-, ^-NH- , -OC (= O)-, -OC (= O ) O-, -OC (= O) NH-, -OC (= O) S-, -C (= O) O-, -C (= O) NH-, -C (= O) S-,- NHC (= O)-, -NHC (= O) O-, -NHC (= O) NH-, -NHC (= O) S-, -S-, -SC (= O)-, -SC (= O) O-, -SC (= O) NH-, or -SC (= O) S-.
Z ^CR21 , Z ^CR22 and Z ^CR23 each independently represent a 5- or 6-membered aromatic ring group, or a 5- or 6-membered non-aromatic ring group.
nCR21, nCR22 and nCR23 each independently represent an integer of 1 to 3.

  In addition, as a compound represented by the partial structure represented by said Formula (CR2), the part represented by said Formula (CR2) among the compounds represented by Formula (D16) mentioned above specifically, Those containing a structure are mentioned.

As the charge transfer complex of the aspect (1), a charge transfer complex composed of two or more discotic compounds selected from compounds containing partial structures represented by the above formula (CR1) and having different partial structures from each other is preferable, X ^CR11 to X ^CR16 and discotic compound comprising a partial structure represented by the above formula (CR1) indicating a is -O- none, X ^CR11 to X ^CR16 both is -C (= O) - above formula representing the More preferred is a charge transfer complex comprising a discotic compound containing a partial structure represented by (CR1).

  In the charge transfer complex according to aspect (1), it is preferable that at least one kind of two or more discotic compounds functioning as an electron donor and an electron acceptor contain a reactive group, and all of them are reactive groups. Is more preferable. Among them, all of the two or more discotic compounds have a polymerizable group, or one represents a polymerizable group and the other is crosslinkable, in that the heat conductivity of the heat conductive material is more excellent. It is further preferable to represent a group, and it is particularly preferable that one of the two or more discotic compounds represents a polymerizable group and the other represents a crosslinkable group.

(Charge transfer complex of aspect (2))
In the charge transfer complex of the above-mentioned aspect (2), a compound in which the electron donor is a discoid compound and the electron acceptor has an oxidation reduction potential of 0 V or more with respect to a saturated calomel electrode (hereinafter, also referred to as "oxidizing agent"). Is a charge transfer complex. That is, the charge transfer complex of the embodiment (2) described above comprises the discotic compound and the oxidizing agent.
The discotic compound is as described above. The discotic compounds may be used alone or in combination of two or more.

The redox potential of the oxidizing agent is measured by cyclic voltammetry using a saturated calomel electrode (saturated calomel reference electrode) as a reference electrode.
Specifically, a voltammogram at a sample concentration of 1 × 10 ^-3 M is measured in acetonitrile containing 0.1 M of tetra-n-ethylammonium perchlorate as a supporting electrolyte, and the half wave potential obtained from this is determined. be able to. More specifically, platinum is used for the working electrode and the measurement is performed at 25 ° C.

  The redox potential of the oxidizing agent is, for example, -0.01 or more, and is preferably 0 V or more, in that the charge transfer complex is more easily formed and the thermal conductivity of the obtained heat conductive material is more excellent. 10 V or more is more preferable. The upper limit of the redox potential is not particularly limited, but is, for example, 0.60 V or less, and preferably 0.50 V or less in that the thermal conductivity of the obtained heat conductive material is more excellent.

  Among these, as the oxidizing agent, a compound represented by the following formula (A) or a compound containing a fluorenone structure is preferable.

In Formula (A), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, an NRNR ¹ group, or a = CR ² R ³ group. When there are a plurality of each of X ¹ and X ² , the plurality of X ¹ and the plurality of X ² may be identical to or different from each other.
Among them, X ¹ and X ² are preferably an oxygen atom or a CRCR ² R ³ group, more preferably a CRCR ² R ³ group.

  m and n respectively independently represent the integer of 0-3, the integer of 1-3 is preferable, 1 or 2 is more preferable, 1 is more preferable. However, the sum of m and n is 2 or more, 2-6 are preferable, 2-4 are more preferable, and 2 is still more preferable.

Each of R ¹ , R ² and R ³ independently represents a hydrogen atom or a substituent. When each of R ¹ , R ² and R ³ is present in plurality, the plurality of R ^{1 's} , the plurality of R ^{2' s} and the plurality of R ³ 's may be the same as or different from each other.
L ¹ and L ² each independently represent a divalent linking group.

The substituent represented by R ¹ , R ² and R ³ may be, for example, an alkyl group (linear, branched or cyclic any of which has 1 to 18 carbon atoms) And 6 to 18 are more preferable), and an alkenyl group (which may be linear, branched or cyclic. The number of carbon atoms is preferably 2 to 18, and more preferably 6 to 18). And an aralkyl group (preferably having 7 to 10 carbon atoms), an aryl group (preferably having 6 to 10 carbon atoms), and a heterocyclic group (any of a single ring structure and a polycyclic structure). Examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom The carbon number in the heterocyclic group is preferably 5 to 18. The heterocyclic group is aromatic or non-aromatic. Any may be.), A halogen atom (fluorine Preferably a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a nitro group, a mercapto group, a hydroxy group or an alkoxy group (the number of carbon atoms is preferably 1 to 18, more preferably 6 to 18). An aryloxy group (preferably having 6 to 10 carbon atoms), an alkylthio group (the number of carbon atoms is preferably 1 to 18, more preferably 6 to 18), and an arylthio group (preferably 6 to 10 carbon atoms). An acyloxy group (the number of carbon atoms is preferably 1 to 18, more preferably 6 to 18), an amino group, an alkylamino group (the number of carbon atoms is preferably 1 to 18, and more preferably 6 to 18). , Carbonamide group (as carbon number, preferably 1 to 18, more preferably 6 to 18), sulfonamide group (as carbon number, 1 to 18 is preferable, 6 to 6). 18 is more preferable), sulfamoylamino group (as carbon number, 0 to 18 is preferable, carbon number 8 to 18 is more preferable), oxycarbonylamino group (as carbon number, 1 to 18 is preferable) , 8 to 18 is more preferable), oxysulfonylamino group (as carbon number is preferably 1 to 18, more preferably 8 to 18), ureido group (as carbon number is preferably 1 to 18) -18 is more preferable), thioureido group (as carbon number, preferably 1-18, more preferably 8-18), acyl group (as carbon number is preferably 1-18, more preferably 8-18) Preferred), an alkoxycarbonyl group (the number of carbon atoms is preferably 1 to 18, more preferably 8 to 18), and a carbamoyl group (the number of carbon atoms is preferably 1 to 18). 8 to 18 are more preferable. ), An alkylsulfonyl group (the number of carbon atoms is preferably 1 to 18, and more preferably 8 to 18), an alkylsulfinyl group (the number of carbon atoms is preferably 1 to 18, and more preferably 8 to 18). Sulfamoyl group, monoalkyl or dialkylsulfamoyl group (the carbon number of the alkyl group is preferably 1 to 18, more preferably 8 to 18), carboxy group (including salt), and sulfo group (including salt) Etc.). The substituent represented by said R < ¹ >, R < ² > and R < ³ > may be further substituted. Among the substituents represented by R ¹ , R ² and R ³ above, a cyano group, an acyl group or an alkoxycarbonyl group is preferable, a cyano group or an alkoxycarbonyl group is more preferable, and a cyano group is more preferable .

L ¹ and L ² each independently represent a divalent linking group.
L ¹ and L ² form a 4-8 membered ring together with (the carbon atom bonded carbon atom bonded to X ^1, and X ²⁾ Formula (A) 2 carbon atoms which is manifested in the.
The divalent linking group represented by the above L ¹ and L ² is not particularly limited, but -C (R ⁴ ) (R ⁵ )-, -C (R ⁶ ) =, -N (R ⁷ )-,- It is preferable that it is the group which combined the group chosen from the group which N =, -C (= O)-, -O-, and -S-. In addition, said R < ⁴ >, R < ⁵ >, R < ⁶ > and R < ⁷ > respectively independently represent a hydrogen atom or a substituent. As a substituent represented by said R < ⁴ >, R < ⁵ >, R < ⁶ > and R < ⁷ >, it is synonymous with the substituent represented by R < ¹ >, R < ² > and R < ³ >, and a preferable aspect is also the same.

The 4- to 8-membered ring formed by L ¹ and L ² and two carbon atoms specified in the formula (A) is not particularly limited, and cyclobutanedione, cyclobutenedione, benzocyclobutenequinone, cyclopentane Dione, cyclopentenedione, cyclopentantriol, cyclopententionyl, indandione, indantrione, tetrahydrofurandione, tetrahydrofuran trione, tetrahydropyrrole dione, tetrahydropyrrole dione, tetrahydrothiophene trione, tetrahydrothiophene dione, tetrahydrothiophene trione, benzoquinone, quinomethane, quinodimethane, quinone diimine, quinone diimine, Thiobenzoquinone, dithiobenzoquinone, naphthoquinone, anthraquinone, dihydroclomenturion, dihydropyridinedione, dihydropyra Gindione, dihydropyrimidinedione, dihydropyridazine dione, dihydrophthalazine dione, dihydroisoquinoline dione, tetrahydroquinoline trione, cycloheptane dione, cycloheptane trione, azacycloheptane trione, diazacycloheptane trione, oxocycloheptane trione, dioxocyclo Heptanetrione, oxoazacycloheptanetrione, cyclooctanedione, cyclooctanetrione, azacyclooctanetrione, diazacyclooctanetrione, oxocyclooctanetrione, dioxocyclooctanetrione, oxoazacyclooctanetrione, cyclooctenedione, cyclooctenedione Octadienedione, dibenzocyclooctenedione and the like can be mentioned. Among them, a six-membered ring is preferable in that the heat conductivity of the heat conductive material is more excellent. In addition, a 4- to 8-membered ring formed by L ¹ and L ² and two carbon atoms specified in Formula (A) is a substituent on the ring (R ⁴ , R ⁵ , R ⁶ , or R ⁷ ) may be bonded to each other. That is, the above 4- to 8-membered ring may form a fused structure with another ring having aromaticity or non-aromaticity (e.g., an alicyclic, aromatic hydrocarbon ring, heterocyclic ring, etc.).

  As a compound represented by Formula (A), the compound represented by a following formula (AI) is preferable.

In formula (A-I), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent. The ^{R 10, R 11, R 12} , and the substituent represented by ^{R 13, R 1, R 2} , and has the same meaning as the substituents represented by R ^3, preferred embodiments are also the same.
R ¹⁰ and R ¹¹ , and R ¹² and R ¹³ may be each independently bonded to each other to form a ring (preferably an aromatic ring). The ring may have a substituent, and examples of the substituent include the same as the substituents represented by R ¹ , R ² and R ³ .
X ¹¹ and X ²² have the same meanings as X ¹ and X ² , and preferred embodiments are also the same.

As the above X ¹¹ and the above X ²² , an oxygen atom or CC (R ¹⁴ ) (R ¹⁵ ) is preferable, and all of X ¹¹ and the above X ²² represent an oxygen atom, or X ¹¹ and the above X ²² There is more preferably represents none ^{= C (R 14) (R} 15). R ¹⁴ and R ¹⁵ each independently represent a halogen atom, a cyano group, an acyl group, an alkoxycarbonyl group, or an alkyl or arylsulfonyl group.
When X ¹¹ and X ²² both represent an oxygen atom, it is preferable that at least two or more of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ be an electron withdrawing group. In the present specification, “electron-withdrawing group” intends a substituent having a positive Hammett σp value, and specifically, a halogen atom, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, a carbamoyl Groups, alkyl or arylsulfonyl groups, and alkyl or arylsulfinyl groups and the like.
When each of X ¹¹ and X ²² represents an oxygen atom, each of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a nitro group, an alkoxy group, Alkylthio group, amino group, alkylamino group, carbonamido group, sulfonamide group, sulfamoylamino group, oxycarbonylamino group, oxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, It is a group selected from the group consisting of an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, and a sulfamoyl group, and preferably at least two or more of them are electron withdrawing groups, each independently a hydrogen atom, Alkyl group having 8 to 18 carbon atoms, halogen atom, cyano group, 8 to 18 carbon atoms And an alkyloxy group having 8 to 18 carbon atoms, a carbonamido group having 8 to 18 carbon atoms, a sulfonamide group having 8 to 18 carbon atoms, a ureido group having 8 to 18 carbon atoms, an acyl group having 8 to 18 carbon atoms, A group selected from the group consisting of an alkoxycarbonyl group having 8 to 18 carbon atoms, a carbamoyl group having 8 to 18 carbon atoms, an alkyl or arylsulfonyl group having 8 to 18 carbon atoms, and an alkyl or arylsulfinyl group having 8 to 18 carbon atoms It is more preferable that at least two or more of these be an electron withdrawing group selected from the group consisting of a halogen atom, a cyano group, an alkyl or aryl sulfonyl group, and an alkyl or aryl sulfinyl group.

  As a compound represented by the said Formula (A-I), the compound represented by a following formula (A-II) is preferable.

In formula (A-II), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a substituent. The substituent represented by R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ has the same meaning as the substituent represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ , and preferred embodiments are also the same. .

  As a compound represented by Formula (A-II), the compound represented by a following formula (A-III) or a following formula (A-IV) is preferable.

In formula (A-III), R ³¹ represents a halogen atom, a cyano group, an alkoxy group, an alkylthio group, a carbonamido group, a sulfonamide group, a ureido group, an acyl group or an alkoxycarbonyl group.
Each of R ⁰³¹ independently represents a hydrogen atom or a substituent. The substituent represented by R ⁰³¹ has the same meaning as the substituent represented by R ¹ , R ² and R ³ , and the preferred embodiments are also the same.
m ⁴ represents an integer of 1 to 4; When there are a plurality of R ^{31 s} and R ^{031 s} , the plurality of R ^{31 s} and the plurality of R ^{031 s} may be the same as or different from each other.

As Formula (A-III), R ³¹ represents a halogen atom, a cyano group, an alkoxy group having 8 to 18 carbon atoms, an acyl group having 8 to 18 carbon atoms, or an alkoxycarbonyl group having 8 to 18 carbon atoms And R ⁰³¹ represents a hydrogen atom or an alkyl group having 8 to 18 carbon atoms, or R ³¹ is a halogen atom, a cyano group, an alkoxy group having 8 to 18 carbon atoms, or 8 to 18 carbon atoms. Or an alkoxycarbonyl group having 8 to 18 carbon atoms, and preferably m ⁴ .

In formula (A-IV) above, R ³² represents a hydrogen atom or a substituent. The substituent represented by R ³² has the same meaning as the substituent represented by R ¹ , R ² and R ³ , and the preferred embodiments are also the same.
m ⁵ represents an integer of 0 to 6; In the case where R ³² there are a plurality, among the plurality of R ^32, it may be the same or different from each other.

As R ³² , a hydrogen atom, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an alkylthio group, a carbonamido group, a sulfonamide group, a ureido group or an acyl group is preferable, and a hydrogen atom having 8 to 18 carbon atoms is preferable. An alkyl group, a halogen atom, a cyano group, an alkoxy group having 8 to 18 carbon atoms, an alkylthio group having 8 to 18 carbon atoms, a carbonamido group having 8 to 18 carbon atoms, a sulfonamide group having 8 to 18 carbon atoms, -18 ureido group or an acyl group having 8 to 18 carbon atoms is more preferable, and a hydrogen atom, an alkyl group having 8 to 18 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, or 8 to 18 carbon atoms An alkoxy group is more preferred, and a hydrogen atom is particularly preferred.

  Below, the specific example of the oxidizing agent represented by Formula (A) is mentioned as an example.

  Moreover, as a compound containing a fluorenone structure, the compound represented by following formula (B) is mentioned, for example.

In Formula (B), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a substituent.
The substituent represented by R ⁴¹ or R ⁴² is not particularly limited, and examples thereof include the same as the substituents represented by R ¹ , R ² and R ³ in the above-mentioned formula (A). The substituent represented by R ⁴¹ or R ⁴² is preferably an electron withdrawing group, and is preferably a halogen atom, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group. And alkyl and arylsulfinyl groups etc., among which nitro is preferred.
In said formula (B), p1 and p2 respectively independently represent the integer of 1-4, and the integer of 1-3 is more preferable.

  Examples of the compound having a fluorenone structure include the following compounds.

  In the charge transfer complex, only one oxidizing agent may be used, or two or more oxidizing agents may be used in combination.

(Method of producing charge transfer complex)
The method of producing the charge transfer complex is not particularly limited. For example, a method of mixing the electron donor and the electron acceptor in a solution, a solution containing the electron donor, and the electron acceptor are included. The method of mixing with a solution etc. are mentioned.
The formation of the charge transfer complex can be identified by UV-visible absorption spectrum measurement, and in detail, it is confirmed by the appearance of a new absorption band (charge transfer absorption band) which does not appear with the electron donor or the electron acceptor alone. it can.

[Other ingredients]
The composition may contain components other than the charge transfer complex described above.
Below, the other component which the composition of this invention may contain is explained in full detail.

<Inorganic substance>
It is preferable that the said composition contains an inorganic substance by the point which the heat conductivity of the heat conductive material obtained is more excellent.

  As the inorganic substance, any inorganic substance conventionally used for an inorganic filler of a heat conductive material may be used. As the inorganic substance, an inorganic oxide or an inorganic nitride is preferable. The inorganic substance may be an inorganic oxynitride. The shape of the inorganic substance is not particularly limited, and may be in the form of particles, in the form of a film, or in the form of a plate. The shape of the particulate inorganic substance may be rice grain, sphere, cube, spindle, scaly, aggregate, or irregular shape.

As the inorganic oxide, for example, 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 oxide Ruthenium (Ru _2), and the like.
The above inorganic oxides may be used alone or in combination of two or more.
The inorganic oxide is preferably titanium oxide, aluminum oxide or zinc oxide.
The inorganic oxide may be an oxide formed by oxidation of a metal prepared as a non-oxide under an environment or the like.

As the inorganic nitride, for example, boron nitride (BN), carbon nitride (C ₃ N ₄ ), silicon nitride (Si ₃ N ₄ ), gallium nitride (GaN), indium nitride (InN), aluminum nitride (AlN), Chromium nitride (Cr ₂ N), copper nitride (Cu ₃ N), iron nitride (Fe ₄ N), iron nitride (Fe ₃ N), lanthanum nitride (LaN), lithium nitride (Li ₃ N), magnesium nitride (Mg ₃ N _2), molybdenum nitride (Mo ₂ N), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (W ₂ N), tungsten nitride (WN _2), yttrium nitride (YN And zirconium nitride (ZrN) and the like.
The above inorganic nitrides may be used alone or in combination of two or more.
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 still more preferably aluminum nitride or boron nitride.

The size of the inorganic substance is not particularly limited, but the average particle diameter of the inorganic substance is preferably 500 μm or less, more preferably 300 μm or less, and 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 is preferably 10 nm or more, and more preferably 100 nm or more in terms of handleability.
As a measuring method of the above-mentioned average particle diameter, 100 inorganic substances are chosen at random using an electron microscope, the particle size (long diameter) of each inorganic substance is measured, and they are determined by arithmetic average. In addition, when using a commercial item, you may use a catalog value.

The inorganic substance may use only 1 type and may use 2 or more types together.
30-95 mass% is preferable with respect to the total solid of a composition, as for content of the inorganic substance in a composition, 35-90 mass% is more preferable, and 40-90 mass% is still more preferable.

<Hardening agent>
The composition may further contain a curing agent.
The type of the curing agent is not particularly limited as long as it is a compound containing a group that reacts with a reactive group that can be optionally contained in the above-described discotic compound. The curing agent is preferably a compound having a functional group selected from the group consisting of a hydroxyl group, an amino group, a thiol group, an isocyanate group, a carboxy group, a (meth) acryloyl group and a carboxylic acid anhydride group. Compounds having a functional group selected from the group consisting of groups, amino groups, and thiol groups are more preferred.
The curing agent preferably contains two or more, and more preferably two or three of the above functional groups.

  Examples of curing agents include amine curing agents, phenol curing agents, guanidine curing agents, imidazole curing agents, naphthol curing agents, acrylic curing agents, acid anhydride curing agents, active ester curing agents, Examples thereof include benzoxazine-based curing agents and cyanate ester-based curing agents. Among them, acrylic curing agents, phenolic curing agents, or amine curing agents are preferable.

  The content of the curing agent in the composition is not particularly limited, but is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass with respect to the total solid content in the composition.

<Hardening accelerator>
The composition may further contain a curing accelerator.
The type of curing accelerator is not limited, and examples thereof include triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, 1-benzyl-2-methylimidazole, and JP-A-2012-67225. Those described in paragraph 0052 can be mentioned.
Although the content in particular of the hardening accelerator in a composition is not restrict | limited, 0.1-20 mass% is preferable with respect to the total solid in a composition.

<Polymerization initiator>
The composition may further contain a polymerization initiator.
In particular, when the discotic compound in the charge transfer complex has a (meth) acryloyl group as a reactive group, the composition is described in paragraph 0062 of JP-A-2010-125782 and in paragraph JP-A-2015-052710. It is preferable to include the polymerization initiator described in 0054.
When the discotic compound in the charge transfer complex has an epoxy group as a reactive group, the composition preferably contains the polymerization initiator described in paragraph 0054 of JP-A-2015-052710.
The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, with respect to the total solid content in the composition. 1-10 mass% is still more preferable.

<Solvent>
The composition may further contain a solvent.
The type of solvent is not particularly limited, and is preferably an organic solvent. Examples of the organic solvent include ethyl acetate, methyl ethyl ketone, dichloromethane, and tetrahydrofuran.

<Method of producing composition>
The method for producing the composition is not particularly limited, and a known method can be adopted. For example, the composition can be produced by mixing the various components described above by a known method. When mixing, various components may be mixed at once or may be mixed one by one.
In addition, the method for producing the composition is (1) a method of mixing and preparing a previously isolated charge transfer complex and an optional additive component, and (2) mixing an electron donor and an electron acceptor in a solution. A charge transfer complex is formed, and then without adding the charge transfer complex, a method of adding any additional component to the above solution, or (3) an electron donor, an electron acceptor, a solvent, and any method The additive components of the above may be mixed to form a charge transfer complex in the mixture.

In the method for producing the above composition, it is preferable that the electron donor and the electron acceptor be mixed in a predetermined ratio in a solution. That is, the method shown to said (2) or (3) is preferable.
The mixing ratio of the electron donor and the electron acceptor is not particularly limited, and the mass content ratio of the electron donor to the electron acceptor (electron donor / electron acceptor) is, for example, 99/1 to 1/99. is there.
In particular, in the charge transfer complex according to aspect (2), when the discotic compound is a compound represented by the formula (D4) (a compound in which the central ring is a triphenylene ring), the mass of the electron donor and the electron acceptor The content ratio (electron donor / electron acceptor) is more excellent in the heat conductivity of the heat conductive material,
85/25 to 99/1 are preferred.

<Method of curing composition>
The composition is preferably a curable composition.
When the composition is a curable composition, the method for curing the composition is not particularly limited, and an optimal method is selected according to the type of reactive group optionally contained in the discotic compound. The curing method may be, for example, a heat curing reaction or a light curing reaction, and a heat curing reaction is preferable.
The heating temperature in the case of the heat curing reaction is not particularly limited. For example, what is necessary is just to select suitably in 50-200 degreeC. Moreover, when performing a thermosetting reaction, you may implement the heat processing which differs in temperature in multiple times.
In the case where the discotic compound exhibits liquid crystallinity, or in the case where the composition exhibits liquid crystallinity, a step of improving the alignment order of liquid crystal components in the composition by heating the composition before carrying out the curing reaction. May be implemented.

  The curing reaction is preferably carried out on a sheet-like composition. Specifically, for example, the composition may be applied, and the resulting coating film may be cured. At that time, pressing may be performed.

The curing reaction may be a semi-curing reaction. That is, the obtained cured product may be in a so-called B-stage state (semi-cured state).
After placing the above-mentioned semi-cured cured product in contact with the device etc., the adhesive property between the layer containing the thermally conductive material which is the cured product and the device can be increased by further curing by heating etc. improves.

<Use>
The composition can be applied to various fields as a heat transfer material. In addition, the shape in particular of a heat conductive material is not restrict | limited, For example, a sheet form may be sufficient.
Hereinafter, the heat conductive material will be described in detail.

(Heat conduction material)
The heat transfer material can be formed using the composition described above. That is, the composition can be used to form a thermally conductive material. In addition, about preparation of the heat conductive material containing hardening reaction, "high thermal conductivity composite material" (CMC publication, Yutaka Takezawa) can be referred.

  The heat conductive material is a material excellent in heat conductivity, and can be used as a heat dissipation material such as a heat dissipation sheet. For example, it can be used for heat dissipation applications of various devices such as power semiconductor devices. More specifically, heat generation from the device can be efficiently dissipated by the heat conduction layer by arranging a heat conduction layer containing the above-mentioned heat conduction material on the device to produce a device with a heat conduction layer.

  The shape of the heat conductive material is not particularly limited, and may be formed into various shapes depending on the application. Typically, the heat transfer material is preferably in the form of a sheet.

  The heat conductive material is preferably a cured product, and may be in a completely cured state or in a semi-cured state (the B-stage state described above). As described above, since it has sufficient thermal conductivity even in a semi-hardened state, it is used as a heat dissipating material disposed at a site where it is difficult for light for photo curing to reach, such as gaps between members of various devices. Can also be used. Moreover, the use as an adhesive which has thermal conductivity is also possible.

The heat conductive material may be used in combination with other members. Specifically, for example, when the heat conductive material is in the form of a sheet, the sheet-like heat conductive material may be laminated on a sheet-like support.
Examples of the sheet-like support include plastic films, metal films, and glass plates.
Examples of the material of the plastic film include polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, silicones, and the like.
As said metal film, a copper film is mentioned, for example.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

[Preparation and Evaluation of Composition]
[Various ingredients]
Below, the various components used by the Example and the comparative example are shown.
<Disc-like compound>
Below, the discotic compound used by the Example and the comparative example is shown.

<Oxidizing agent>
The oxidizing agents used in the examples are shown below.

(Redox potential)
The redox potentials of the above compounds (IV) to (VI) were measured by cyclic voltammetry using a saturated calomel electrode (saturated calomel reference electrode) as a reference electrode. Specifically, a voltammogram of a sample concentration of 1 × 10 ^-3 M is measured in acetonitrile containing 0.1 M of tetra-n-ethylammonium perchlorate as a supporting electrolyte, and it is determined as a half wave potential obtained from this The In addition, platinum was used for a working electrode, and the measurement was performed at 25 degreeC.
The redox potentials of the compounds (IV) to (VI) are shown in Table 1.

<Polymerization initiator>
The polymerization initiators used in Examples and Comparative Examples are shown below.
"Radical based polymerization initiator": VAm-110 (manufactured by Wako Pure Chemical Industries, Ltd.)
"Acid-based polymerization initiator": SI-B5 (manufactured by Sanshin Chemical Co., Ltd.)

<Solvent>
CPO (cyclopentanone) was used as a solvent.

<Inorganic filler>
The following fillers were used as inorganic fillers.
"PTX-60": Aggregated boron nitride (average particle size: 60 μm, manufactured by Momentive)
"AA-3": alumina (average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd.)
“AA-04”: alumina (average particle size: 0.4 μm, manufactured by Sumitomo Chemical Co., Ltd.)

Example 1
<Preparation of composition>
The various components shown in the following Table 1 were mixed in the order of CPO (cyclopentanone), an electron donor, an electron acceptor, and a polymerization initiator. Composition 1 was obtained by processing the obtained mixture for 5 minutes with a rotation revolution mixer (manufactured by THINKY, Awatori Neritaro ARE-310).
Also, the final solid content of Composition 1 was adjusted with CPO so that the solid content concentration described in Table 1 (described in the “solvent” column) was obtained.

(Confirmation of charge transfer complex formation)
The formation of the charge transfer complex was identified by UV-visible absorption spectrum measurement using the obtained composition. In detail, it was confirmed by the appearance of a new absorption band (charge transfer absorption band) which does not appear with the electron donating compound alone or the electron accepting compound alone on the long wavelength side. The peak wavelength (nm) of the charge transfer absorption band is shown in Table 1 as "the peak wavelength (nm) derived from CT".

<Preparation of heat conductive material>
Next, using an applicator, the composition 1 is uniformly applied on the release surface of a polyester film (NP-100A Panac, film thickness 100 μm), and the coating 1 is left by standing in air for 1 hour. Obtained.
Next, the coated film surface of the coated film 1 is covered with another polyester film, and hot pressed under air (heat plate temperature 160 ° C., treated at pressure 12 MPa for 30 minutes, and further 190 ° C., pressure 12 MPa for 2 hours) The coating film was cured by treatment with to obtain a resin sheet. The polyester films on both sides of the resin sheet were peeled off to obtain a thermally conductive sheet 1 having an average film thickness of 419 μm.

<Evaluation of thermal conductivity>
Thermal conductivity evaluation was performed using the heat conductive sheet 1. The thermal conductivity was measured by the following method, and the thermal conductivity was evaluated according to the following criteria.

(Measurement of thermal conductivity (W / m · k))
(1) The thermal diffusivity in the thickness direction of the thermally conductive sheet 1 was measured using "Eyephase Mobile 1u" manufactured by Eyephase.
(2) The specific gravity of the thermally conductive sheet 1 was measured by the Archimedes method (using a “solid specific gravity measurement kit”) using a balance “XS 204” manufactured by METTLER TOLEDO.
(3) The specific heat of the thermally conductive sheet 1 at 25 ° C. was determined using “DSC 320/6200” manufactured by Seiko Instruments Inc. under a temperature rising condition of 10 ° C./min.
(4) The thermal conductivity of the thermally conductive sheet 1 was calculated by multiplying the obtained thermal diffusivity by specific gravity and specific heat.

(Evaluation criteria)
“A”: 1.20 W / m · K or more “B”: 0.80 W / m · K or more and 1.20 W / m · K or less “C”: 0.40 W / m · K or more 0.80 W / m · K Less than K "D": less than 0.40 W / m · K Results are shown in Table 1.

[Examples 2 to 20, Comparative Examples 1 to 12]
By the procedure similar to Example 1, each composition of Examples 2-20 shown to following Table 1 and following Table 2 and Comparative Examples 1-12 was obtained. In Examples 2 to 20, it was confirmed that the charge transfer complex was formed in the composition, but in Comparative Examples 1 to 12, the charge transfer complex was not formed in the composition.
In addition, the final solid content of the composition was adjusted with CPO so that the solid content concentration described in Table 1 and Table 2 (described in the “solvent” column) was obtained.
Further, in the same manner as in Example 1, thermal conductive sheets 2 to 20 and comparative thermal conductive sheets 1 to 12 were produced from each composition obtained, and a thermal conductivity evaluation test was carried out. The results are shown in Tables 1 and 2.

Tables 1 and 2 are shown below.
In Table 1 and Table 2, "content (mass%)" means content (mass%) of various components with respect to the total solid in a composition.
In the “structure” described in Table 1, the electron accepting compound and the electron donating compound used are discotic compounds, or are represented by the above-mentioned formula (A) or the above-mentioned formula (B) Indicate whether it is an oxidizing agent.
The "radical type polymerization initiator" described in Tables 1 and 2 intends VAm-110 (manufactured by Wako Pure Chemical Industries, Ltd.), and the "acid type polymerization initiator" means SI-B5 (Mixin Intended for Chemical Company.
The “mass content ratio of the electron donor compound to the electron acceptor compound” described in Table 1 is the mixing ratio of the electron donor compound to the electron acceptor compound added to the composition for a heat conductive material (electron donor The term “body compound content / electron acceptor compound content” is intended.
Further, “film thickness [μm]” described in Tables 1 and 2 means the average film thickness of the heat conductive sheet.

From the results of Table 1 and Table 2, it was confirmed that the thermally conductive material obtained from the composition for forming thermally conductive material of the example is excellent in thermal conductivity.
Further, from the comparison between Example 1 and Example 2, the composition for forming a heat conductive material contains a charge transfer complex formed from a discotic compound and a compound having a redox potential of 0 V or more for a saturated calomel electrode. In the case, it was confirmed that the heat conductivity is excellent.
Further, from the comparison between Example 1 and Example 7, it is apparent that the composition for forming a heat conductive material is a charge transfer complex formed from a discotic compound and a compound having an oxidation reduction potential of 0.50 V or less with respect to a saturated calomel electrode. When it contains, it was confirmed that it is excellent by thermal conductivity.
Further, from the comparison of Example 1, Example 3, and Example 4 and the comparison with Example 9, Example 10, and Example 11, the composition for forming a thermally conductive material has a polymerizable group-containing disc. It was confirmed that the heat conductivity is superior when the obtained heat conductive material is a cured product containing a cyclic compound.
Further, from the comparison of Example 1, Example 5, Example 5, Example 6, Example 8, and Example 12, the composition for forming a heat conductive material has an oxidation reduction potential relative to a saturated carmel electrode of 0 V or more. A charge transfer complex formed from a certain compound and a discotic compound (a compound represented by the above-mentioned formula (D4)) having a triphenylene compound as a skeleton, and having a redox potential of 0 V with respect to the saturated carmel electrode When it is a composition formed by mixing the mass content ratio of the compound which is the above, and the said disc-like compound with 85/25-99/1, it was confirmed that it is excellent by thermal conductivity.
In addition, comparing Example 4, Example 11, and Example 16, although the thermal conductivity is "C" evaluation in any of the examples, it can be obtained by the composition for forming a heat conductive material of Example 16. The thermally conductive material resulted in a slightly inferior result as compared with Example 4 and Example 11. From this result, when the discotic compound forming the charge transfer complex in the composition for forming a heat conductive material is a compound represented by the formula (D4) or a compound represented by the formula (D16), the thermal conductivity is It was confirmed that the better.
Further, from the comparison of Example 17 to Example 20, the composition for forming a heat conductive material contains a charge transfer complex consisting of two or more discotic compounds different in structure from one another, and one of the discotic compounds is When it contains a polymeric group (for example, an epoxy group) and the other of the said discotic compound contains a crosslinkable group (for example, a hydroxyl group), it was confirmed that it is excellent by thermal conductivity.
On the other hand, it became clear from the results of Table 2 that the heat conductive material obtained from the composition for forming a heat conductive material of the comparative example does not satisfy the desired performance.

[Example 21]
The various components shown in Table 3 below were mixed in the order of CPO (cyclopentanone), an electron donor, an electron acceptor, a polymerization initiator, and an inorganic filler. The composition 21 was obtained by processing the obtained mixture for 5 minutes with a rotation revolution mixer (manufactured by THINKY, Awatori Neritaro ARE-310).
Also, the final solid content of the composition 21 was adjusted with CPO so as to have the solid content concentration described in Table 3 (described in the “solvent” column).

Next, using an applicator, the composition 21 is uniformly applied on the release surface of a polyester film (NP-100A Panac, film thickness 100 μm), and the coating 21 is left by standing in air for 1 hour. Obtained.
Next, the coated film surface of the coated film 21 is covered with another polyester film, and hot pressed under air (heat plate temperature 160 ° C., treated at pressure 12 MPa for 30 minutes, and further 190 ° C., pressure 12 MPa for 2 hours) The coating film was cured by treatment with to obtain a resin sheet. The polyester films on both sides of the resin sheet were peeled off to obtain a thermally conductive sheet 21 having an average film thickness of 421 μm.

<Evaluation of thermal conductivity>
Thermal conductivity evaluation was performed using the heat conductive sheet 21. The thermal conductivity was measured by the following method, and the thermal conductivity was evaluated according to the following criteria.

(Measurement of thermal conductivity (W / m · k))
(1) The thermal diffusivity in the thickness direction of the thermally conductive sheet 1 was measured using "Eyephase Mobile 1u" manufactured by Eyephase.
(2) The specific gravity of the thermally conductive sheet 1 was measured by the Archimedes method (using a “solid specific gravity measurement kit”) using a balance “XS 204” manufactured by METTLER TOLEDO.
(3) The specific heat of the thermally conductive sheet 1 at 25 ° C. was determined using “DSC 320/6200” manufactured by Seiko Instruments Inc. under a temperature rising condition of 10 ° C./min.
(4) The thermal conductivity of the thermally conductive sheet 1 was calculated by multiplying the obtained thermal diffusivity by specific gravity and specific heat.

(Evaluation criteria)
"A": 12 W / m · K or more "B": 9 W / m · K or more 12 W / m · K "C": 6 W / m · K or more 9 W / m · K or less "D": 6 W / m · Less than K The results are shown in Table 3.

[Examples 22 to 31, Comparative Examples 13 to 18]
Moreover, the thermally conductive sheets 22-31 and the thermally conductive sheets 13-18 for comparison were produced from each composition obtained, and the thermal conductivity evaluation test similar to Example 21 was implemented. The results are shown in Table 3.

Table 3 is shown below.
In Table 3, "content (mass%)" means content (mass%) of various components with respect to the total solid in a composition.
The "radical type polymerization initiator" described in Table 3 intends VAm-110 (manufactured by Wako Pure Chemical Industries, Ltd.), and the "acid type polymerization initiator" is SI-B5 (manufactured by Sanshin Chemical Co., Ltd.) Intended).
The “mass content ratio of the electron donor compound to the electron acceptor compound” described in Table 3 is the mixing ratio of the electron donor compound to the electron acceptor compound added to the composition for a heat conductive material (electron donor The term “body compound content / electron acceptor compound content” is intended.
Further, “film thickness [μm]” described in Table 3 means the average film thickness of the heat conductive sheet.

From the results of Table 3, it was confirmed that when the composition for forming a heat transfer material contains an inorganic substance, the obtained heat transfer material is further excellent in heat conductivity.
On the other hand, it is clear from the results of Table 3 that the heat conductive material obtained from the composition for forming a heat conductive material of the comparative example does not satisfy the criteria of the product of the example.

Claims (14)

Containing charge transfer complexes,
The composition for heat-conductive material formation in which the said charge transfer complex contains a discotic compound at least.   The composition for forming a heat transfer material according to claim 1, wherein the charge transfer complex is composed of the discotic compound and a compound having a redox potential of 0 V or more with respect to a saturated calomel electrode.   The composition for forming a heat transfer material according to claim 2, wherein the charge transfer complex is composed of the discotic compound and a compound having a redox potential relative to a saturated calomel electrode of 0 V or more and 0.50 V or less. The composition for forming a thermally conductive material according to claim 2 or 3, wherein the discotic compound is selected from the group consisting of a compound represented by the following formula (D4) and a compound represented by the following formula (D16) .

In the formulae, each L independently represents a divalent linking group. Each Q independently represents a hydrogen atom or a substituent.

In formula, ^A2X , ^A3X , and ^A4X respectively independently represent -CH = or -N =. R ^17X, R ^18X, and R ^19X are independently * - represents the _{^{(X 211X -Z 21X) n21X -L}} 21X -Q. * Represents the bonding position with the central ring. X ²¹¹ X is each independently a single bond, -O-, -C (= O)-, -NH-, -OC (= O)-, -OC (= O) O-, -OC (= O) NH-, -OC (= O) S-, -C (= O) O-, -C (= O) NH-, -C (= O) S-, -NHC (= O)-, -NHC ( OO—, —NHC (= O) NH—, —NHC (= O) S—, —S—, —SC (= O) —, —SC (= O) O—, —SC (= O) And n represents an —NH— or —SC (= O) S—.
Z ^21X each independently represents a 5- or 6-membered aromatic ring group, or a 5- or 6-membered non-aromatic ring group.
L ^{21 X} represents a single bond or a divalent linking group.
Each Q independently represents a hydrogen atom or a substituent.
n21X represents an integer of 0 to 3; If n21X is 2 or more, there are a plurality (X ^211X -Z ^21X) may be the same or different.   The composition for heat-conductive material formation of any one of Claims 2-4 in which the said disc-like compound contains a polymeric group.   The composition for forming a heat transfer material according to claim 1, wherein the charge transfer complex is composed of two or more discotic compounds having different structures.   The composition for forming a heat transfer material according to claim 6, wherein at least one of the discotic compounds contains a polymerizable group.   The composition for forming a heat conductive material according to claim 7, wherein one of the discotic compounds contains a polymerizable group and the other contains a crosslinkable group. The charge transfer complex is at least two selected from the group consisting of a discotic compound containing a partial structure represented by the following formula (CR1) and a discotic compound containing a partial structure represented by the following formula (CR2) Consisting of discotic compounds, and
The composition for forming a heat transfer material according to any one of claims 6 to 8, wherein the partial structures of the two or more discotic compounds are different from each other.

In the formula, each of X ^{CR11 to} X ^CR16 independently represents a single bond, -O-, -C (= O)-, -NH-, or -S-. * Represents a bonding position.

In the formulae, X ^CR21 , X ^CR22 and X ^CR23 each independently represent a single bond, -O-, -C (= O)-, ^-NH- , -OC (= O)-, -OC (= O ) O-, -OC (= O) NH-, -OC (= O) S-, -C (= O) O-, -C (= O) NH-, -C (= O) S-,- NHC (= O)-, -NHC (= O) O-, -NHC (= O) NH-, -NHC (= O) S-, -S-, -SC (= O)-, -SC (= O) O-, -SC (= O) NH-, or -SC (= O) S-.
Z ^CR21 , Z ^CR22 and Z ^CR23 each independently represent a 5- or 6-membered aromatic ring group, or a 5- or 6-membered non-aromatic ring group.
nCR21, nCR22 and nCR23 each independently represent an integer of 1 to 3. The charge transfer complex is a discotic compound including a partial structure represented by the formula (CR1) in which all of the X ^CR11 to the X ^CR16 represent —O—, and all of the X ^CR11 to the X ^CR16 are — The composition for heat conductive material formation of Claim 9 which consists of a disc-like compound containing the partial structure represented by said Formula (CR1) which represents C (= O)-.   Furthermore, the composition for heat conductive material formation of any one of Claims 1-10 containing an inorganic substance.   The heat conductive material formed using the composition for heat conductive material formation of any one of Claims 1-11.   The heat transfer material according to claim 12, which is in the form of a sheet.   A device with a thermally conductive layer, comprising a device and a thermally conductive layer comprising a thermally conductive material according to claim 12 or 13 disposed on the device.