阅读说明：本技术 组合物、导热材料、带导热层的器件及导热材料的制造方法 (Composition, heat conduction material, device with heat conduction layer and manufacturing method of heat conduction material ) 是由 人见诚一 高桥庆太 新居辉树 吉田有次 于 2018-12-18 设计创作，主要内容包括：本发明的第1课题在于提供一种能够提供导热性优异的固化物即导热材料的组合物。并且,本发明的第2课题在于提供一种由上述组合物形成的导热材料及带导热层的器件。并且,本发明的第3课题在于提供一种使用了上述组合物的导热材料的制造方法。本发明的组合物含有包含含活性氢官能团的固化剂及包含与上述含活性氢官能团反应的反应性基团的主剂,上述主剂及上述固化剂分别在单独的状态下在150℃以下的温度下显示液晶性。(The present invention addresses the 1 st object of providing a composition that can provide a heat conductive material that is a cured product having excellent heat conductivity. Another object of the present invention is to provide a heat conductive material and a thermally conductive device each made of the composition. Another object of the present invention is to provide a method for producing a heat conductive material using the composition. The composition of the present invention contains a curing agent containing an active hydrogen-containing functional group and a main agent containing a reactive group that reacts with the active hydrogen-containing functional group, and the main agent and the curing agent each exhibit liquid crystallinity in a separate state at a temperature of 150 ℃ or lower.)

1. A composition comprising:

a curing agent comprising an active hydrogen-containing functional group; and

a host comprising a reactive group that reacts with the active hydrogen-containing functional group,

the curing agent and the main agent each exhibit liquid crystallinity at a temperature of 150 ℃ or lower in a separate state.

2. The composition of claim 1, wherein,

the curing agent and the main agent each exhibit nematic liquid crystallinity at a temperature of 150 ℃ or lower in a single state.

3. The composition of claim 1 or 2,

the main agent contains a cyclopolymerizing group.

4. The composition according to any one of claims 1 to 3,

the curing agent is a disc-shaped compound.

5. The composition according to any one of claims 1 to 4,

the main agent is a disc-shaped compound.

6. The composition according to any one of claims 1 to 5,

the curing agent and the main agent are both disc-shaped compounds.

7. The composition according to any one of claims 4 to 6,

the discotic compound is a discotic compound selected from the group comprising:

a discotic compound having a partial structure represented by the following formula (CR4) and a discotic compound having a partial structure represented by the following formula (CR16),

[ chemical formula 1]

(CR4)

Wherein denotes a bonding site,

[ chemical formula 2]

In the formula, a plurality of X^211XEach independently represents a single bond, -O-, -C (═ O) -, -NH-, -OC (═ O) O-, -OC (═ O) NH-, -OC (═ O) S-, -C (═ O) O-, -C (═ O) NH-, -C (═ O) S-, -NHC (═ O) O-, -NHC (═ O) NH-, -NHC (═ O) S-, -SC (═ O) O-, -SC (═ O) NH-, or-SC (═ O) S-,

multiple Z^21XEach independently represents an aromatic ring group of a 5-membered ring or a 6-membered ring or a non-aromatic ring group of a 5-membered ring or a 6-membered ring,

A^2X、A^3Xand A^4XAll represent-CH ═ CH,

n21X each independently represents an integer of 0 to 3,

denotes the bonding site.

8. The composition of any one of claims 1 to 7, further comprising an inorganic substance.

9. The composition of claim 8, wherein,

the inorganic matter is inorganic nitride or inorganic oxide.

10. The composition of claim 8 or claim 9,

the inorganic substance has an average particle diameter of 20 μm or more.

11. The composition of claim 8 or claim 9,

the inorganic substance is boron nitride.

12. The composition according to any one of claims 1 to 11, which exhibits nematic liquid crystallinity.

13. The composition of any one of claims 1 to 12, for use in forming a thermally conductive material.

14. A method of making a thermally conductive material, comprising:

a step 1 of forming a composition layer using the composition according to any one of claims 1 to 13;

step 2 of heating the composition layer to a temperature of 150 ℃ or lower to align the curing agent and the main agent, while the curing agent and the main agent in the composition layer both exhibit liquid crystallinity; and

and 3, curing the composition layer.

15. The method of manufacturing a thermally conductive material of claim 14,

the step 3 is a curing step by a thermosetting method.

16. A thermally conductive material formed using the composition of any one of claims 1 to 13.

17. The thermally conductive material of claim 16, which immobilizes a nematic liquid crystal phase.

18. The thermally conductive material of claim 16 or 17, which is sheet-like.

19. A thermally conductive device, comprising:

device and

a thermally conductive layer comprising the thermally conductive material of any of claims 16-18 disposed on the device.

Technical Field

The invention relates to a composition, a heat conducting material, a device with a heat conducting layer and a manufacturing method of the heat conducting material.

Background

In recent years, miniaturization of power semiconductor devices used in various electrical devices such as personal computers, general household electrical appliances, and automobiles has been rapidly advanced. With miniaturization, it becomes difficult to control heat generated from a power semiconductor device having a higher density.

To cope with such a problem, a heat conductive material that promotes heat dissipation from the power semiconductor device is used.

For example, patent document 1 discloses "an epoxy resin obtained by a reaction of an epoxy resin monomer having a mesogenic skeleton and 2 glycidyl groups in 1 molecule and a dihydric phenol compound having 2 hydroxyl groups as substituents on 1 benzene ring, and having a number average molecular weight of 600 to 2500 as measured by gel permeation chromatography," as an epoxy resin having excellent thermal conductivity. ".

Prior art documents

Patent document

Patent document 1: international publication No. 2016/104772

Disclosure of Invention

Technical problem to be solved by the invention

As a result of studies on the epoxy resin (heat conductive material) described in patent document 1, the present inventors have found that the heat conductivity does not satisfy the level required in recent years, and further improvement is required.

Accordingly, an object of the present invention is to provide a composition that can provide a cured product (heat conductive material) having excellent heat conductivity.

Another object of the present invention is to provide a heat conductive material and a device with a heat conductive layer, each of which is formed from the composition.

Another object of the present invention is to provide a method for producing a heat conductive material using the composition.

Means for solving the technical problem

The present inventors have conducted extensive studies to achieve the above object and found that the above object can be achieved by using a compound exhibiting liquid crystallinity for both a main agent and a curing agent, and completed the present invention.

That is, the following configuration was found to solve the above problems.

[ 1] A composition comprising:

a curing agent comprising an active hydrogen-containing functional group; and

a main agent containing a reactive group which reacts with the active hydrogen-containing functional group,

the curing agent and the main agent each exhibit liquid crystallinity at a temperature of 150 ℃ or lower in a single state.

[ 2] the composition according to [ 1], wherein,

the curing agent and the main agent each exhibit nematic liquid crystallinity at a temperature of 150 ℃ or lower in a single state.

[ 3] the composition according to [ 1] or [ 2], wherein,

the main agent contains a cyclopolymerizable group.

[ 4] the composition according to any one of [ 1] to [ 3], wherein,

the curing agent is a disk-shaped compound.

[ 5] the composition according to any one of [ 1] to [ 4], wherein,

the main agent is a discotic compound.

[ 6] the composition according to any one of [ 1] to [ 5], wherein,

the curing agent and the main agent are both discotic compounds.

[ 7] the composition according to any one of [ 4] to [ 6], wherein,

the discotic compound is a discotic compound selected from the group consisting of a discotic compound having a partial structure represented by the formula (CR4) described later and a discotic compound having a partial structure represented by the formula (CR16) described later.

The composition according to any one of [ 1] to [ 7], which further comprises an inorganic substance.

[ 9] the composition according to [ 8], wherein,

the inorganic substance is inorganic nitride or inorganic oxide.

[ 10] the composition according to [ 8] or [ 9], wherein,

the inorganic substance has an average particle diameter of 20 μm or more.

[ 11] the composition according to [ 8] or [ 9], wherein,

the inorganic substance is boron nitride.

[ 12] the composition according to any one of [ 1] to [ 11], which shows a nematic liquid crystal property.

[ 13] the composition according to any one of [ 1] to [ 12], which is used for forming a heat conductive material.

A method of making a thermally conductive material, comprising:

step 1 of forming a composition layer using the composition according to any one of [ 1] to [ 13 ];

a step 2 of heating the composition layer at a temperature of 150 ℃ or lower to align the curing agent and the main agent, the curing agent and the main agent both exhibiting liquid crystallinity in the composition layer; and

and a step 3 of curing the composition layer.

[ 15] the method for producing a heat conductive material according to [ 14], wherein,

the step 3 is a curing step by a thermosetting method.

[ 16] A heat conductive material formed using the composition according to any one of [ 1] to [ 13 ].

The thermally conductive material according to [ 16], which is formed by fixing a nematic liquid crystal phase.

[ 18] the heat conductive material according to [ 16] or [ 17], which is in a sheet form.

A thermally conductive device comprising a device and a thermally conductive layer comprising the thermally conductive material of any one of [ 16] to [ 18] disposed on the device.

Effects of the invention

The present invention can provide a composition that can provide a cured product (heat conductive material) having excellent heat conductivity.

Further, the present invention can provide a heat conductive material formed from the composition and a device with a heat conductive layer.

Further, the present invention can provide a method for producing a heat conductive material using the composition.

Detailed Description

The composition, the heat conductive material, the device with a heat conductive layer, and the method for producing the heat conductive material of the present invention will be described in detail below.

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value.

In the present specification, an oxirane group is a functional group also referred to as an epoxy group, and for example, a group in which 2 adjacent carbon atoms of a saturated hydrocarbon ring group are bonded through an oxo group (-O-) to form an oxirane ring, or the like is also included in the oxirane group.

In the present specification, the expression "(meth) acryloyl group" means "either or both of an acryloyl group and a methacryloyl group". The expression "(meth) acrylamide group" means "one or both of an acrylamide group and a methacrylamide group".

In the present specification, the kind of the substituent, the position of the substituent and the number of the substituents in the case of "optionally having a substituent" are not particularly limited. The number of the substituents may be, for example, 1 or 2 or more. Examples of the substituent include a non-metallic atomic group having a valence of 1 other than a hydrogen atom, and can be selected from the following substituent group Y.

Substituent group Y:

halogen atom (-F, -Br, -Cl, -I), hydroxyl group, amino group, carboxyl group and conjugated base thereof, carboxylic anhydride group, isocyanate group, unsaturated polymerizable group, oxirane 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-dialkylamino group, N-arylamino group, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N-dialkylcarbamoyloxy group, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, N-diarylcarbamoyloxy group, N-alkyl-N, Alkylsulfoxy, arylsulfonyl, acylthio, acylamino, N-alkylamido, N-arylamido, ureido, N '-alkylureido, N' -dialkylureido, N '-arylureido, N' -diarylureido, N '-alkyl-N' -arylureido, N-alkylureido, N-arylureido, N '-alkyl-N-alkylureido, N' -alkyl-N-arylureido, N '-dialkyl-N-alkylureido, N' -dialkyl-N-arylureido, N '-aryl-N-alkylureido, N' -aryl-N-arylureido, N '-diaryl-N-alkylureido, N' -arylureido, N ', N' -diaryl-N-arylureido, N '-alkyl-N' -aryl-N-alkylureido, N '-alkyl-N' -aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, formyl, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N-dialkylcarbamoyl, N-arylcarbamoyl, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO)₃H) And their conjugate bases, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-acylsulfamoyl and their conjugate bases, N-alkylsulfonylsulfamoyl (-SO)₂NHSO₂(alkyl)) and its conjugated base, N-arylsulfonylaminosulfonyl (-SO)₂NHSO₂(aryl)) and a conjugated base thereof, an N-alkylsulfonylcarbamoyl group (-CONHSO)₂(alkyl)) and the conjugated base thereof, N-arylsulfonylcarbamoyl (-CONHSO)₂(aryl)) and a conjugated basic group thereof, an alkoxysilyl group (-Si (alkyl))₃) Aryloxysilyl (-Si (aryl))₃) Hydroxysilyl (-Si (OH))₃) And its conjugated base group, phosphono (-PO)₃H₂) And its conjugated basic group, dialkyl phosphonyl (-PO)₃(alkyl)₂) Diaryl phosphonyl (-PO)₃(aryl)₂) Alkyl aryl phosphonyl (-PO)₃(alkyl) (aryl)), monoalkyl phosphono (-PO)₃H (alkyl)) and its conjugated base, monoarylphosphono (-PO)₃H (aryl)) and conjugate base thereof, phosphonoxy (-OPO)₃H₂) And its conjugated basic group, dialkyl phosphonoxy (-OPO)₃(alkyl)₂) Diaryl phosphonyloxy (-OPO)₃(aryl)₂) Alkyl aryl phosphonoxy (-OPO)₃(alkyl) (aryl)), monoalkylphosphonoxy (-OPO)₃H (alkyl)) and its conjugate base, monoarylphosphonoxy (-OPO)₃H (aryl)), and its conjugate base, cyano, nitro, aryl, alkenyl, alkynyl, and alkyl.

And, these substituents may form a ring when the substituents are bonded to each other or to the substituted group, if possible.

Examples of the unsaturated polymerizable group include a (meth) acryloyl group, a (meth) acrylamide group, and substituents represented by Q1 to Q7 shown below.

[ chemical formula 1]

[ composition ]

The composition of the present invention comprises:

a curing agent comprising an active hydrogen-containing functional group; and

a main agent containing a reactive group which reacts with the active hydrogen-containing functional group,

the curing agent and the main agent each exhibit liquid crystallinity at a temperature of 150 ℃ or lower in a single state.

In the present specification, "exhibits liquid crystallinity at a temperature of 150 ℃ or lower in a single state" means that a compound functioning as a curing agent or a compound functioning as a main agent exhibits liquid crystallinity in a monomer state (in other words, in a state of not being mixed with other components) at a temperature of 150 ℃ or lower. The lower limit is not particularly limited, and is, for example, room temperature (25 ℃ C.) or higher.

The phrase "exhibiting liquid crystallinity at a temperature of 150 ℃ or lower" means that the compound may exhibit a liquid crystal phase at least in a temperature range of 150 ℃ or lower. That is, the above-mentioned compound corresponds to the following case: (1) a case where a phase transition temperature of a crystal phase-liquid crystal phase is 150 ℃ or less and a phase transition temperature of an isotropic phase-liquid crystal phase is 150 ℃ or less or (2) a case where a phase transition temperature of a crystal phase-liquid crystal phase is 150 ℃ or less and a phase transition temperature of an isotropic phase-liquid crystal phase exceeds 150 ℃.

The liquid crystallinity of the above compound can be confirmed by observation with a polarized light microscope or differential scanning calorimetry.

The present inventors have now found that, in a composition comprising a main agent and a curing agent capable of reacting with the main agent, when the main agent and the curing agent are each a compound exhibiting liquid crystallinity at a temperature which is independently not higher than a predetermined temperature, the thermal conductivity of the resulting cured product (thermally conductive material) is significantly improved.

When the thermally conductive material is formed using the composition, the coating film (composition layer) of the composition is preferably heated to a temperature at which both the curing agent and the main agent in the composition layer exhibit liquid crystallinity (preferably nematic liquid crystallinity) and the curing reaction of the curing agent and the main agent does not substantially proceed, and the curing agent and the main agent are aligned and then thermally cured in this state. In addition, the thermal curing reaction is usually initiated by temperatures in excess of 150 ℃. Therefore, in the above composition, the curing agent and the main agent exhibit liquid crystallinity at a temperature of 150 ℃ or lower, and thereby the alignment of the liquid crystal component occurs preferentially to the thermal curing reaction, and a cured product (heat conductive material) having a high order degree is obtained. Further, by setting the curing reaction to the thermosetting treatment, the reaction between the main agent exhibiting each liquid crystallinity and the curing agent can be further accelerated as compared with the case of the photocuring treatment, and it has been confirmed that the obtained heat conductive material is more excellent in heat conductivity.

In addition, when both the curing agent and the main agent are disk-shaped compounds, the obtained cured product has more excellent thermal conductivity. The discotic compound is considered to have more excellent thermal conductivity because a plurality of side chains containing a reactive group can be arranged radially with respect to the central core (i.e., the thermal conduction path is easily extended).

The curing agent and the main agent preferably exhibit a nematic liquid crystal phase in a temperature range of 150 ℃. The thermally conductive material formed from the composition of the present invention has a high thermal conductivity to the extent required for a thermally conductive sheet even if it is a nematic liquid crystal phase having a relatively low degree of order.

Also, when the composition of the present invention contains an inorganic substance, the thermal conductivity of the thermally conductive material is further improved. In addition, even in the case where the composition of the present invention does not contain an inorganic substance (in other words, in the case where the composition is formed only of an organic substance), the thermally conductive material has high thermal conductivity to the extent necessary for the thermally conductive sheet.

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

[ curing agent ]

The composition of the present invention comprises a curing agent. The curing agent contains an active hydrogen-containing functional group and exhibits liquid crystallinity in a single state at a temperature of 150 ℃ or less.

In the present specification, "active hydrogen" refers to a hydrogen atom directly bonded to a nitrogen atom, an oxygen atom, or a sulfur atom.

The active hydrogen-containing functional group contained in the curing agent is not particularly limited as long as it is a functional group containing the active hydrogen, and is preferably, for example, an amino group, a thiol group, a hydroxyl group, or a carboxyl group.

The type of active hydrogen-containing functional group contained in the curing agent is appropriately selected depending on the type of reactive group in the main agent used together.

Examples of the reactive group that can be used when the active hydrogen-containing functional group is an amino group include an oxirane group, an oxetanyl group, a carboxyl group, a halobenzyl group, an isocyanate group, an aldehyde group, and a carbonyl group.

Examples of the reactive group that can be used when the active hydrogen-containing functional group is a thiol group include a vinyl group, an oxirane group, an oxetanyl group, a halobenzyl group, a carboxylic anhydride group, an isocyanate group, and an alkoxysilyl group.

Examples of the reactive group that can be used when the active hydrogen-containing functional group is a hydroxyl group include an oxirane group, an oxetanyl group, a halobenzyl group, a carboxylic anhydride group, an isocyanate group, and an alkoxysilyl group.

Examples of the reactive group that can be used when the active hydrogen-containing functional group is a carboxyl group include an oxirane group, an oxetanyl group, a halobenzyl group, a cyanate group, an isocyanate group, and an aziridine group.

The curing agent may be used alone to exhibit liquid crystallinity at a temperature of at least 150 ℃. In the curing agent, the phase transition temperature of the crystalline phase-liquid crystal phase is preferably less than 150 ℃ and the phase transition temperature of the isotropic phase-liquid crystal phase is 200 ℃ or less, and more preferably 130 ℃ or less and the phase transition temperature of the isotropic phase-liquid crystal phase is 180 ℃ or less, from the viewpoint of more excellent thermal conductivity of the heat conductive material.

The liquid crystal phase of the curing agent is preferably a nematic liquid crystal phase in a temperature range of 150 ℃.

The curing agent may be used in 1 kind alone, or 2 or more kinds may be used simultaneously.

The content of the curing agent in the composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 20 to 70% by mass, based on the total solid content of the composition. The solid component may be a component constituting the heat conductive material, and may be contained in the solid component even in a liquid state.

The curing agent is preferably a compound having a rod-like structure (rod-like compound) or a compound having a disk-like structure (disk-like compound), and more preferably a disk-like compound from the viewpoint of more excellent thermal conductivity of the heat conductive material.

As a reason why the heat conductivity of the heat conductive material is more excellent when the discotic compound is used as the curing agent, it is considered that the rod-like compound can conduct heat only linearly (one-dimensionally), whereas the discotic compound can conduct heat planarly (two-dimensionally) in the normal direction. That is, when a disk-shaped compound is used as the curing agent, more heat conduction paths are formed, and as a result, the thermal conductivity is considered to be improved.

Further, the use of the disc-shaped compound improves the heat resistance of the cured product of the composition.

The rod-like compound and the disk-like compound will be described below.

< rod-shaped Compound >

When the curing agent is a rod-like liquid crystal compound, examples of the rod-like structure include methyleneamines, azoxides, cyanobiphenyls, cyanobenzenes, benzoates, cyclohexanecarboxylic acid benzoates, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitrile. Not only the low molecular liquid crystal compound as above but also a high molecular liquid crystal compound can be used. The polymer liquid crystal compound is a polymer compound obtained by polymerizing a low-molecular liquid crystal compound having a rod-like structure and having a low-molecular reactive group.

Also, the above-mentioned rod-like compound preferably contains 2 or more active hydrogen-containing functional groups.

The preferred form of the curing agent in the case of a rod-like compound will be described later together with the preferred form of the main agent in the case of a rod-like compound.

< discotic compound >

The disc-shaped compound has at least in sections a disc-shaped structure.

The discotic structure has at least an alicyclic or aromatic ring. In particular, when the discotic structure has an aromatic ring, the discotic compound can form a columnar structure by forming a packing structure under pi-pi interaction between molecules.

Specific examples of the discotic structure include triphenylene structures described in angelw.chem.int.ed.2012, 51, 7990-.

The discotic compound preferably contains 3 or more active hydrogen-containing functional groups. A cured product of a composition containing a discotic compound having 3 or more active hydrogen-containing functional groups tends to have a high glass transition temperature and high heat resistance. This is because the discotic compound is less susceptible to the characteristics of the mesogenic portion than the rod-like compound even if it contains 3 or more active hydrogen-containing functional groups. The number of active hydrogen-containing functional groups contained in the discotic compound is preferably 8 or less, and more preferably 6 or less.

Specific examples of the discotic compound include c.destrand et al, mol.crysr.liq.cryst, vol.71, page 111 (1981); quartely Chemical Reviews, Chemical society of Japan, No.22, Chemistry of Liquid Crystal, Chapter 5, Chapter 10, part 2 (1994); b.kohne et al, angelw.chem.soc.chem.comm., page 1794 (1985); j.zhanget al., j.am.chem.soc., vol.116, page 2655 (1994) and japanese patent No. 4592225. Examples of the discotic compound include triphenylene structures described in Angew. chem. int. Ed.2012, 51, 7990-7993 and Japanese patent application laid-open No. 7-306317, and 3-substituted benzene structures described in Japanese patent application laid-open No. 2O07-002220 and Japanese patent application laid-open No. 2010-244038.

The preferred form of the curing agent in the case of a disk-shaped compound will be described later together with the preferred form of the main agent in the case of a disk-shaped compound.

[ Main agent ]

The compositions of the present invention comprise a base. The main agent contains a reactive group that reacts with the active hydrogen-containing functional group in the curing agent, and exhibits liquid crystallinity in a single state at a temperature of 150 ℃ or less.

The reactive group means a polymerizable group and a crosslinkable group, and among them, a polymerizable group is preferable.

The type of the polymerizable group is not particularly limited, and a known polymerizable group can be used, and from the viewpoint of more excellent reactivity and thermal conductivity of the thermally conductive material, a functional group capable of an addition polymerization reaction is preferable, a polymerizable ethylenically unsaturated group or a cyclopolymerizable group is more preferable, and a cyclopolymerizable group is even more preferable.

Specifically, from the viewpoint of more excellent thermal conductivity of the heat conductive material, the polymerizable group is preferably a (meth) acryloyl group, a vinyl group, an oxirane group, or an oxetane group, and more preferably an oxirane group or an oxetane group. The hydrogen atom in each of the above groups may be substituted with another substituent such as a halogen atom.

Examples of the crosslinkable group include a carboxylic anhydride group, a halogen atom, an isocyanate group, a cyano group, an aziridine group, a thioisocyanate group, and an aldehyde group.

The host agent may exhibit liquid crystallinity in a temperature range of at least 150 ℃ or less in a single state, but from the viewpoint of more excellent thermal conductivity of the thermally conductive material, it is more preferable that the phase transition temperature of the crystal phase-liquid crystal phase is less than 150 ℃ and the phase transition temperature of the isotropic phase-liquid crystal phase is 250 ℃ or less, and it is more preferable that the phase transition temperature of the crystal phase-liquid crystal phase is 100 ℃ or less and the phase transition temperature of the isotropic phase-liquid crystal phase is 250 ℃ or less.

The liquid crystal phase of the host agent in the temperature range of 150 ℃ or lower is preferably a nematic liquid crystal phase.

The above-mentioned main agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the main agent in the composition is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass, based on the total solid content of the composition.

The main agent is preferably a rod-like compound or a disk-like compound, and more preferably a disk-like compound from the viewpoint of more excellent thermal conductivity of the heat conductive material.

As a reason why the heat conductivity of the heat conductive material is more excellent when the disk-shaped compound is used as a main component, it is considered 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. That is, when a disk-shaped compound is used as a main agent, more heat conduction paths are formed, and as a result, the thermal conductivity is considered to be improved.

Further, the use of the disc-shaped compound improves the heat resistance of the cured product of the composition.

In addition, from the viewpoint of more excellent compatibility and more excellent thermal conductivity of the heat conductive material, both the curing agent and the main agent are preferably rod-shaped compounds or both disc-shaped compounds, and more preferably both disc-shaped compounds. Among them, both the curing agent and the main agent are preferably a disk-shaped compound having a partial structure represented by the following formula (CR4) or a disk-shaped compound having a partial structure represented by the following formula (CR 16).

< rod-shaped Compound >

When the host agent is a rod-like liquid crystal compound, examples of the rod-like structure include methyleneamines, azoxides, cyanobiphenyls, cyanobenzenes, benzoates, cyclohexanecarboxylic acid benzoates, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitrile. Not only the low molecular liquid crystal compound as above but also a high molecular liquid crystal compound can be used. The polymer liquid crystal compound is a polymer compound obtained by polymerizing a rod-like compound having a reactive group of a low molecule.

Also, the main agent preferably contains 2 or more reactive groups.

The preferred form of the main agent in the case of a rod-like compound will be described later.

< discotic compound >

The disc-shaped compound has at least in sections a disc-shaped structure.

The discotic structure has at least an alicyclic or aromatic ring. In particular, when the discotic structure has an aromatic ring, the discotic compound can form a columnar structure by forming a packing structure under pi-pi interaction between molecules.

Specific examples of the discotic structure include triphenylene structures described in Angew. chem. int. Ed.2012, 51, 7990-7993 or Japanese patent application laid-open No. 7-306317, and 3-substituted benzene structures described in Japanese patent application laid-open Nos. 2007-002220 and 2010-244038.

The discotic compound preferably comprises more than 3 reactive groups. A cured product of a composition containing a discotic compound having 3 or more reactive groups tends to have a high glass transition temperature and high heat resistance. This is because the discotic compound is less susceptible to the characteristics of the mesogenic portion than the rod-like compound even if it contains 3 or more reactive groups. The number of reactive groups contained in the discotic compound is preferably 8 or less, and more preferably 6 or less.

Specific examples of the discotic compound include c.destrand et al, mol.crysr.liq.cryst, vol.71, page 111 (1981); quartely Chemical Reviews, Chemical society of Japan, No.22, Chemistry of Liquid Crystal, Chapter 5, Chapter 10, part 2 (1994); b.kohne et al, angelw.chem.soc.chem.comm., page 1794 (1985); j.zhanget al., j.am.chem.soc., vol.116, page 2655 (1994) and japanese patent No. 4592225. Examples of the discotic compound include triphenylene structures described in Angew. chem. int. Ed.2012, 51, 7990-7993 and Japanese patent application laid-open No. 7-306317, and 3-substituted benzene structures described in Japanese patent application laid-open Nos. 2007-002220 and 2010-244038.

The preferred form of the base compound in the case of a disk-like compound will be described later.

[ structures of curing agent and Main agent ]

Hereinafter, preferred embodiments of the case where the curing agent is a rod-shaped compound and the case where the main component is a rod-shaped compound, and preferred embodiments of the case where the curing agent is a disk-shaped compound and the case where the main component is a disk-shaped compound will be described in detail.

[ preferred embodiments in the case where the curing agent is a rod-like compound and the main agent is a rod-like compound ]

When the curing agent is a rod-like compound and the main agent is a rod-like compound, the rod-like compound is preferably a rod-like compound represented by the following formula (XXI).

Formula (XXI): q¹-L¹¹¹-A¹¹¹-L¹¹³-M-L¹¹⁴-A¹¹²-L¹¹²-Q²

In the formula, L¹¹¹、L¹¹²、L¹¹³And L¹¹⁴Each independently represents a single bond or a 2-valent linking group. A. the¹¹¹And A¹¹²Each independently represents a linking group (spacer group) having a valence of 2 and having 1 to 20 carbon atoms. M represents a mesogenic group. And, when the formula (XXI) is a curing agent，Q¹And Q²Independently represent an active hydrogen-containing functional group, and when formula (XXI) is a main agent, Q¹And Q²Each independently represents a reactive group.

In addition, the definition of the active hydrogen-containing functional group and the definition of the reactive group are as described above, respectively.

As L¹¹¹、L¹¹²、L¹¹³And L¹¹⁴The 2-valent linking group preferably includes-O-, -S-, -C (═ O) -, -NR¹¹²-、-C(＝O)-O-、-O-C(＝O)-O-、-C(＝O)-NR¹¹²-、-NR¹¹²-C(＝O)-、-O-C(＝O)-、-CH₂-O-、-O-CH₂-、-O-C(＝O)-NR¹¹²-、-NR¹¹²-C (═ O) -O-and-NR¹¹²-C(＝O)-NR¹¹²-a linking group having a valence of 2 in the group of (a). R is as defined above¹¹²Is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.

A¹¹¹And A¹¹²Represents a linking group having a valence of 2 and having 1 to 20 carbon atoms. Among them, an alkylene group, an alkenylene group or an alkynylene group having 1 to 12 carbon atoms is preferable, and an alkylene group having 1 to 12 carbon atoms is more preferable.

The linking group having a valence of 2 is preferably linear and may contain an oxygen atom or a sulfur atom which is not adjacent to each other. The linking group having a valence of 2 may have a substituent, and 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.

Examples of the mesogenic group represented by M include known mesogenic groups. Among them, a group represented by the following formula (XXII) is preferable.

Formula (XXII): - (W)¹-L¹¹⁵)_n-W²-

In the formula, W¹And W²Each independently represents a 2-valent cyclic alkylene group, a 2-valent cyclic alkenylene group, an arylene group, or a 2-valent heteroatom-containing cyclic group. L is¹¹⁵Represents a single bond or a 2-valent linking group. n represents 1, 2 or 3.

As W¹And W²Examples thereof include 1, 4-cyclohexenediyl, 1, 4-cyclohexanediyl, and 1, 4-phenylenePyrimidine-2, 5-diyl, pyridine-2, 5-diyl, 1, 3, 4-thiadiazole-2, 5-diyl, 1, 3, 4-oxadiazole-2, 5-diyl, naphthalene-2, 6-diyl, naphthalene-1, 5-diyl, thiophene-2, 5-diyl, pyridazine-3, 6-diyl, and the like. In the case of 1, 4-cyclohexanediyl, the compound may be either one of the trans-isomer and cis-isomer, or a mixture thereof in any ratio. Among them, the trans-isomer is preferred.

W¹And W²Each may have a substituent. Examples of the substituent include those exemplified in the above substituent group Y, and more specifically, examples thereof include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), a cyano group, an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., formyl group, acetyl group, etc.), an alkoxycarbonyl group having 1 to 10 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), an acyloxy group having 1 to 10 carbon atoms (e.g., acetoxy group, propionyloxy group, etc.), a nitro group, a trifluoromethyl group, and a difluoromethyl group.

As L¹¹⁵The linking group having a valence of 2 as represented above includes the above-mentioned L¹¹¹～L¹¹⁴Specific examples of the 2-valent linking group include, for example, -C (═ O) -O-, -O-C (═ O) -, -CH₂-O-and-O-CH₂-and the like.

The following examples show preferred skeletons among the basic skeletons of the mesogenic group represented by the above formula (XXII). These skeletons may be substituted with the above-mentioned substituents.

[ chemical formula 2]

[ chemical formula 3]

Further, the compound represented by the formula (XXI) can be synthesized by referring to the method described in Japanese patent application laid-open No. Hei 11-513019 (WO 97/000600).

The rod-like compound may be a monomer having a mesogenic group as described in Japanese patent application laid-open No. 11-323162 and Japanese patent application laid-open No. 4118691.

[ preferred embodiment when the curing agent is a disk-shaped compound and when the main agent is a disk-shaped compound ]

In the case where the curing agent is a disk-shaped compound and the main agent is a disk-shaped compound, from the viewpoint of more excellent thermal conductivity of the heat conductive material, the disk-shaped compound is preferably a disk-shaped compound having a partial structure represented by the following formulae (CR1) to (CR16), and more preferably a disk-shaped compound having a partial structure represented by the formula (CR4) or the formula (CR 16).

In the formulae (CR1) to (CR16), a symbol denotes a bonding site.

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

In the formula (CR16), a plurality of X' s^211XEach independently represents a single bond, -O-, -C (═ O) -, -NH-, -OC (═ O) O-, -OC (═ O) NH-, -OC (═ O) S-, -C (═ O) O-, -C (═ O) NH-, -C (═ O) S-, -NHC (═ O) O-, -NHC (═ O) NH-, -NHC (═ O) S-, -SC (═ O) O-, -SC (═ O) NH-, or-SC (═ O) S-.

Multiple Z^21XEach independently represents an aromatic ring group of a 5-membered ring or a 6-membered ring or a non-aromatic ring group of a 5-membered ring or a 6-membered ring,

A^2X、A^3Xand A^4XEach independently represents-CH or-N, preferably a^2X、A^3XAnd A^4XAll represent-CH ═ c.

Each of the plurality of n21X independently represents an integer of 0 to 3, preferably an integer of 1 to 3.

Among these, the disk-shaped compound is more preferably a compound represented by any one of formulae (D1) to (D16) shown below, from the viewpoint of more excellent thermal conductivity of the heat conductive material. The formulae (D1) to (D16) correspond to discotic compounds having the formulae (CR1) to (CR16) as partial structures, respectively. In the following formulae, "-LQ" represents "-L-Q", and "QL-" represents "Q-L-".

The following first describes the formulae (D1) to (D15).

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

In the formulae (D1) to (D15), L represents a linking group having a valence of 2.

From the viewpoint of more excellent thermal conductivity of the heat conductive material, each L is preferably a group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -C (═ O) -, -NH-, -O-, -S-, and a combination thereof, and more preferably a group in which 2 or more groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -C (═ O) -, -NH-, -O-, and-S-are combined. Further, L is more preferably a 2-valent linking group containing at least one of — C (═ O) -O-and-O-C (═ O) -.

The number of carbon atoms of the alkylene group is preferably 1 to 12. The number of carbon atoms of the alkenylene group is preferably 2 to 12. The number of carbon atoms of the arylene group is preferably 10 or less. The alkylene group, the alkenylene group and the arylene group may further have a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 6 carbon atoms), a halogen atom, a cyano group, an alkoxy group (preferably having 1 to 6 carbon atoms), an acyloxy group (preferably having 1 to 6 carbon atoms), and the like.

Examples of L are shown below. In the following examples, the left-hand connecting bond is bonded to the central core (hereinafter, also simply referred to as "central ring") of the compound represented by any one of formulae (D1) to (D15), and the right-hand connecting bond is bonded to Q.

AL means alkylene or alkenylene and AR means arylene.

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：-NH-AL-O-

L107：-AL-C(＝O)-O-AL-AR-

L108：-AL-C(＝O)-O-AR-

L109：-O-AL-NH-AR-

L110：-O-AL-O-C(＝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-O-C(＝O)-AL-S-AR-

L134：-AL-C(＝O)-O-AL-O-C(＝O)-AL-S-AL-

L135：-AL-C(＝O)-O-AL-O-AR-

L136：-O-AL-O-C(＝O)-AR-

L137：-O-C(＝O)-AL-O-AR-

L138：-O-C(＝O)-AR-O-AL-O-AR-

In the formulae (D1) to (D15), Q independently represents a hydrogen atom or a substituent.

When the formula (D1) to (D15) is a curing agent, examples of the substituent include an active hydrogen-containing functional group and the groups exemplified in the substituent group Y, and among them, an active hydrogen-containing functional group is preferable. Among them, in the formulae (D1) to (D15), 1 or more of Q are active hydrogen-containing functional groups, and among them, from the viewpoint that the heat conductive material is more excellent in heat conductivity, 3 or more of Q are preferred active hydrogen-containing functional groups, and more preferably all Q are active hydrogen-containing functional groups. In addition, the definition of the active hydrogen-containing functional group is as described above.

When the formulae (D1) to (D15) are main agents, examples of the substituent include a reactive group and the groups exemplified in the substituent group Y, and among them, a reactive group is preferable. Among them, in the formulae (D1) to (D15), 1 or more of Q are reactive groups, and among them, from the viewpoint of more excellent thermal conductivity of the heat conductive material, 3 or more of Q are preferred as reactive groups, and all of Q are more preferred as reactive groups. In addition, the reactive groups are as defined above.

Among the compounds represented by the formulae (D1) to (D15), the compound represented by the formula (D4) is preferable from the viewpoint that the heat conductivity of the heat conductive material is more excellent.

As the compound represented by the formula (D4), a compound represented by the formula (XI) is preferable from the viewpoint that the thermal conductivity of the thermally conductive material is more excellent.

[ chemical formula 13]

In the formula (XI), R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently represent X-X¹¹-L¹¹-P¹¹or-X¹²-L¹²-Y¹²。

In addition, represents a bonding position to a triphenylene ring.

R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶In the total number of the above 2 is ^ -X¹¹-L¹¹-P¹¹Preferably 3 or more are X-X¹¹-L¹¹-P¹¹。

Among them, R is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material¹¹And R¹²At least one of R and R¹³And R¹⁴And R is¹⁵And R¹⁶Any 1 or more of them is-X¹¹-L¹¹-P¹¹More preferably R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶All are X-X¹¹-L¹¹-P¹¹. In addition, R is more preferable¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶All the same.

X¹¹Each independently represents a single bond, -O-, -C (═ O) -, -NH-, -OC (═ O) O-, -OC (═ O) NH-, -OC (═ O) S-, -C (═ O) O-, -C (═ O) NH-, -C (═ O) S-, -NHC (═ O) O-, -NHC (═ O) NH-, -NHC (═ O) S-, -SC (═ O) O-, -SC (═ O) NH-, or-SC (═ O) S-.

Wherein, X¹¹Each is independently preferably — O-, -OC (═ O) O-, -OC (═ O) NH-, -C (═ O) O-, -C (═ O) NH-, -NHC (═ O) -or-NHC (═ O) O-, more preferably-O-, -OC (═ O) -, -C (═ O) O-, -OC (═ O) NH-, or-C (═ O) NH-, and further preferably-C (═ O) O-.

L¹¹Each independently represents a single bond or a 2-valent linking group.

Examples of the linking group having a valence of 2 include-O-, -OC (-O) -, -C (-O) O-, -S-, -NH-, alkylene (having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 7 carbon atoms), arylene (having preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms), and a group composed of a combination thereof.

Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl 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, an anthracenylene group and the like, and a 1, 4-phenylene group is preferable.

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

It is also preferable that the alkylene group and the arylene group are unsubstituted. Among them, the alkylene group is preferably unsubstituted.

-X¹¹-L¹¹-represents a 2-valent group.

as-X¹¹-L¹¹Examples of-are L101 to L138, which are examples of L described above.

When formula (XI) is a curing agent, P¹¹Represents an active hydrogen-containing functional group. In addition, the definition of the active hydrogen-containing functional group is as described above. In addition, when P is¹¹When it is a hydroxyl group, L is preferably¹¹Comprising an arylene group, the arylene group being in contact with P¹¹And (4) bonding.

When formula (XI) is the main agent, P¹¹Represents a reactive group. In addition, the reactive groups are as defined above.

X¹²And X¹¹Similarly, the preferred conditions are the same.

L¹²And L¹¹Similarly, the preferred conditions are the same.

-X¹²-L¹²-represents a 2-valent group.

as-X¹²-L¹²Examples of-are L101 to L138, which are examples of L described above.

Y¹²Represents 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 which 1 or 2 or more methylene groups are replaced by-O-, -S-, -NH-, -N (CH)₃) -, -C (═ O) -, -OC (═ O) -, or-C (═ O) O-.

When Y is¹²Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms in which 1 or 2 or more methylene groups are replaced by-O-, -S-, -NH-, -N (CH)₃)-、When a group substituted by-C (═ O) -, -OC (═ O) -, or-C (═ O) O-, Y¹²1 or more of the hydrogen atoms contained in (a) may be substituted with a halogen atom.

Y¹²Preferably 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, wherein 1 or 2 or more methylene groups are replaced by-O-, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, a C2-20 alkyl group consisting of- (OC-)₂H₄)_m1A group represented by-H (wherein m1 represents an integer of 1 or more) or a group having 3 to 20 carbon atoms represented by- (OC)₃H₆)_m2A group represented by-H (wherein m2 represents an integer of 1 or more).

As specific examples of the compound represented by the formula (XI), there can be mentioned the compounds described in paragraphs 0028 to 0036 of Japanese patent application laid-open No. 7-281028, paragraphs 0016 to 0018 of Japanese patent application laid-open No. 7-306317, paragraphs 0016 to 0018 of Japanese patent application laid-open No. 2005-156822, paragraphs 0067 to 0072 of Japanese patent application laid-open No. 2006-301614, and pages 330 to 333 of the liquid crystal journal (published in 12 years YAMAZENCORPORATION).

The compound represented by the formula (XI) can be synthesized according to the methods described in Japanese patent application laid-open Nos. 7-306317, 7-281028, 2005-156822 and 2006-301614.

Next, formula (D16) will be described.

[ chemical formula 14]

In the formula (D16), A^2X、A^3XAnd A^4XEach independently represents-CH or-N. Wherein A is^2X、A^3XAnd A^4XEach is preferably-CH ═ CH. In other words, the central ring of the discotic compound is also preferably a benzene ring.

R^17X、R^18XAnd R^19XEach independently represents — (X)^211X-Z^21X)_n21X-L^21X-Q. Denotes the bonding site to the central ring.

X^211XEach independently represents a single bond, -O-, -C (═ O) -, -NH-, -OC (═ O) O-, -OC (═ O) NH-, -OC (═ O) S-, -C (═ O) O-, -C (═ O) NH-, -C (═ O) S-, -NHC (═ O) O-, -NHC (═ O) NH-, -NHC (═ O) S-, -SC (═ O) O-, -SC (═ O) NH-, or-SC (═ O) S-.

Z^21XEach independently represents an aromatic ring group of a 5-membered ring or a 6-membered ring or a non-aromatic ring group of a 5-membered ring or a 6-membered ring,

L^21Xrepresents a single bond or a 2-valent linking group.

Q is the same as Q in the formulae (D1) to (D15), and the preferred embodiment is the same.

n21X represents an integer of 0 to 3. When n21X is 2 or more, there are plural (X)^211X-Z^21X) May be the same or different.

The compound represented by the formula (D16) is preferably a compound represented by the formula (XII).

[ chemical formula 15]

In the formula (XII), A²、A³And A⁴Each independently represents-CH or-N. Wherein A is²、A³And A⁴Each is preferably-CH ═ CH. In other words, the central ring of the discotic compound is also preferably a benzene ring.

R¹⁷、R¹⁸And R¹⁹Each independently represents — (X)²¹¹-Z²¹)_n21-L²¹-P²¹Or: - (X)²²¹-Z²²)_n22-Y²². Denotes the bonding site to the central ring.

R¹⁷、R¹⁸And R¹⁹More than 2 of the total number of the derivatives are — (X)²¹¹-Z²¹)_n21-L²¹-P²¹. From the viewpoint of more excellent thermal conductivity of the heat conductive material, R¹⁷、R¹⁸And R¹⁹Preferably all are — (X)²¹¹-Z²¹)_n21-L²¹-P²¹. In addition, R¹⁷、R¹⁸And R¹⁹Preferably all of them are identical.

X²¹¹And X²²¹Each independently represents a single bond, -O-, -C (═ O) -, -NH-, -OC (═ O) O-, -OC (═ O) NH-, -OC (═ O) S-, -C (═ O) O-, -C (═ O) NH-, -C (═ O) S-, -NHC (═ O) O-, -NHC (═ O) NH-, -NHC (═ O) S-, -SC (═ O) O-, -SC (═ O) NH-, or-SC (═ O) S-.

Wherein, as X²¹¹And X²²¹Each is independently preferably a single bond, -O-, -C (═ O) O-, or-OC (═ O) -.

Z²¹And Z²²Each independently represents an aromatic ring group having a 5-or 6-membered ring or a non-aromatic ring group having a 5-or 6-membered ring, and examples thereof include a 1, 4-phenylene group, a 1, 3-phenylene group, an aromatic heterocyclic group and the like.

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. The aromatic ring group and the non-aromatic ring group are preferably unsubstituted.

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

[ chemical formula 16]

In the formula, represents and X²¹¹Or X²²¹The site of bonding. Is represented by²¹Or Y²²The site of bonding. A. the⁴¹And A⁴²Each independently represents a methine group or a nitrogen atom. X⁴Represents an oxygen atom, a sulfur atom, a methylene group or an imino group.

A⁴¹And A⁴²Preferably at least one is a nitrogen atom, more preferably two are nitrogen atoms. And, X⁴Preferably an oxygen atom.

When n21 and n22 are 2 or more, a plurality of (X) s are present²¹¹-Z²¹) And (X)²²¹-Z²²) May be the same or different.

L²¹Each independently represents a single bond or a 2-valent linking group with L in the above formula (XI)¹¹The meaning is the same. As L²¹Preferably, the group is-O-, -OC (-O) -, -C (-O) O-, -S-, -NH-, alkylene (the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 7.), arylene (the number of carbon atoms is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10.), or a combination thereof.

When n21 is 1 or more, it is represented by the formula-L²¹Examples of "L" include L101 to L138 which are examples of L in the above formulae (D1) to (D15).

When formula (XII) is a curing agent, P²¹Represents an active hydrogen-containing functional group. In addition, the definition of the active hydrogen-containing functional group is as described above. In addition, when P is²¹When it is a hydroxyl group, L is preferably²¹Comprising an arylene group, the arylene group being in contact with P²¹And (4) bonding.

When formula (XII) is the main agent, P²¹Represents a reactive group. In addition, the reactive groups are as defined above.

Y²²Represents 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 which 1 or 2 or more methylene groups are replaced by-O-, -S-, -NH-, -N (CH)₃) -, -C (═ O) -, -OC (═ O) -, or-C (═ O) O-. As Y²²With Y in the formula (XI)¹²The preferred forms of (3) are the same.

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

Preferred examples of the compound represented by the formula (XII) include the following compounds.

In the following structural formula, R represents-L²¹-P²¹。

[ chemical formula 17]

For details and specific examples of the compound represented by the formula (XII), reference can be made to the descriptions in paragraphs 0013 to 0077 of Japanese patent application laid-open No. 2010-244038, the contents of which are incorporated herein.

The compound represented by the formula (XII) can be synthesized according to the methods described in Japanese patent application laid-open Nos. 2010-244038, 2006-076992 and 2007-002220.

The discotic compound is preferably a compound having a hydrogen-bonding functional group, from the viewpoint of enhancing stacking by decreasing the electron density to easily form a columnar aggregate. Examples of the hydrogen-bonding functional group include — OC (═ O) NH-, -C (═ O) NH-, -NHC (═ O) O-, -NHC (═ O) NH-, -NHC (═ O) S-, and-SC (═ O) NH-.

Specific examples of the curing agent are shown below, but the curing agent is not limited thereto.

(curing agent)

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

Specific examples of the base compound will be described below, but the base compound is not limited thereto.

(Main agent)

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ other Components ]

The composition may contain components other than the curing agent and the main agent.

The other components that the composition of the present invention may contain are described in detail below.

< inorganic substance >

The composition preferably contains an inorganic substance from the viewpoint that the obtained thermally conductive material is more excellent in thermal conductivity.

As the inorganic substance, any inorganic substance conventionally used for inorganic fillers of heat conductive materials can be used. The inorganic substance is preferably an inorganic oxide or an inorganic thin substance. 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, a film or a plate. Examples of the shape of the particulate inorganic material include rice grains, spheres, cubes, spindles, scales, aggregates and irregular shapes.

Examples of the inorganic oxide include zirconium oxide (ZrO)₂) Titanium oxide (TiO)₂) Silicon oxide (SiO)₂) Alumina (Al)₂O₃) Iron oxide (Fe)₂O₃、FeO、Fe₃O₄) Copper oxide (CuO, Cu)₂O), zinc oxide (ZnO), yttrium oxide (Y)₂O₃) Niobium oxide (Nb)₂O₅) Molybdenum oxide (MoO)₃) Indium oxide (In)₂O₃、In₂O), tin oxide (SnO)₂) Tantalum oxide (Ta)₂O₅) Tungsten oxide (WO)₃、W₂O₅) Lead oxide (PbO )₂) Bismuth oxide (Bi)₂O₃) Cerium oxide (CeO)₂、Ce₂O₃) Antimony oxide (Sb)₂O₃、Sb₂O₅) Germanium oxide (GeO)₂GeO), lanthanum oxide (La)₂O₃) And ruthenium oxide (RuO)₂) And the like.

The inorganic oxide may be used in 1 kind alone, or 2 or more kinds may be used simultaneously.

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 oxidation of a metal prepared as a non-oxide under the environment or the like.

Examples of the inorganic nitride include Boron Nitride (BN) and carbon nitride (C)₃N₄) Silicon nitride (Si)₃N₄) Gallium nitride (GaN), indium nitride (InN), aluminum nitride (AlN), chromium nitride (Cr)₂N), copper nitride (Cu)₃N), iron nitride (Fe)₄N), iron nitride (Fe)₃N), lanthanum nitride (Lan), lithium nitride (Li)₃N), magnesium nitride (Mg)₃N₂) Molybdenum nitride (Mo)₂N), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (W)₂N), tungsten nitride (WN)₂) Yttrium Nitride (YN), zirconium nitride (ZrN), and the like.

The inorganic nitride may be used in 1 kind alone, or 2 or more kinds may be used simultaneously.

The inorganic nitride preferably contains aluminum atoms, boron atoms, or silicon atoms, more preferably aluminum nitride, boron nitride, or silicon nitride, still more preferably aluminum nitride or boron nitride, and particularly preferably boron nitride.

The size of the inorganic substance is not particularly limited, but from the viewpoint of more excellent dispersibility of the inorganic substance, 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. The lower limit is not particularly limited, but is preferably 10nm or more, more preferably 100nm or more, from the viewpoint of handling property.

As the average particle diameter of the inorganic substance, a catalog value is adopted when a commercially available product is used. When there is no index value, 100 inorganic substances are randomly selected by using an electron microscope as a method for measuring the average particle diameter, the particle diameter (major axis) of each inorganic substance is measured, and the particle diameter is arithmetically averaged to obtain the average particle diameter.

The inorganic substances may be used alone in 1 kind or in combination of 2 or more kinds.

When the composition contains an inorganic substance, the content of the inorganic substance in the composition is preferably 1 to 90% by mass, more preferably 5 to 90% by mass, and still more preferably 10 to 90% by mass, based on the total solid content of the composition.

When the composition contains an inorganic substance, the composition more preferably contains at least inorganic particles having an average particle diameter of 20 μm or more (preferably 50 μm or more) from the viewpoint that the thermal conductivity of the thermally conductive material is more excellent.

Further, when the composition contains an inorganic substance, the composition more preferably contains at least boron nitride from the viewpoint that the thermal conductivity of the thermal conductive material is more excellent.

< curing accelerators >

The composition may further comprise a curing accelerator.

The kind of the curing accelerator is not limited, and examples thereof include triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, 1-benzyl-2-methylimidazole, and the curing catalyst described in paragraph 0052 of Japanese patent laid-open No. 2012-067225.

When the composition contains a curing accelerator, the content of the curing accelerator in the composition is not particularly limited, but is preferably 0.1 to 20% by mass relative to the total solid content in the composition.

< polymerization initiator >

The composition may further comprise a polymerization initiator.

In particular, when the main agent has a (meth) acryloyl group as a reactive group, the composition preferably contains a polymerization initiator described in paragraph 0062 of jp 2010-125782 and paragraph 0054 of jp 2015-052710.

When the composition contains a polymerization initiator, the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 50% by mass relative to the total solid content in the composition.

< solvent >

The composition may further comprise a solvent.

The kind of the solvent is not particularly limited, and an organic solvent is preferable. Examples of the organic solvent include ethyl acetate, methyl ethyl ketone, methylene chloride, and tetrahydrofuran.

[ method for producing composition ]

The method for producing the composition is not particularly limited, and the composition can be produced by a known method, for example, by mixing the above-mentioned various components by a known method. When mixing, the respective components may be mixed at once, or may be mixed in sequence.

Further, the composition of the present invention preferably exhibits nematic liquid crystallinity. When the main agent and the curing agent each independently exhibit nematic liquid crystallinity, a composition containing both of them generally exhibits nematic liquid crystallinity in the same manner. Among them, in the composition of the present invention, it is preferable that the phase transition temperature of the crystal phase-liquid crystal phase is 130 ℃ or less, more preferably 130 ℃ or less and 250 ℃ or less.

[ method for producing Heat conductive Material (method for curing composition) ]

The method for producing the heat conductive material of the present invention will be described below.

The method for producing a heat conductive material of the present invention includes at least the following steps 1 to 3.

Step 1: a step of forming a composition layer using the composition

And a step 2: a step of aligning the curing agent and the main agent by heating the composition layer at a temperature of 150 ℃ or lower, the curing agent and the main agent both exhibiting liquid crystallinity in the composition layer

Step 3: and curing the composition layer.

Hereinafter, the steps 1 to 3 will be described in detail.

< step 1>

Step 1 is a step of forming a composition layer using the composition of the present invention. Specifically, the method comprises a step of applying the composition to a substrate to form a composition layer.

(substrate)

The substrate is a plate supporting a layer of the composition described later. In addition, the substrate is typically peeled from the composition layer after curing of the composition layer.

The material constituting the substrate is not particularly limited, and examples thereof include a plastic film, a metal film, and a glass plate.

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, and silicones.

Examples of the metal thin film include a copper film.

The thickness of the substrate is not particularly limited, but is preferably 5 to 2000 μm, and more preferably 10 to 1000 μm, from the viewpoint of thinning and handleability.

The thickness is an average thickness, and is a value obtained by measuring the thickness of any 5 points of the substrate and arithmetically averaging these. The thickness of the reflective layer is measured by the same method as described below.

(step of Process 1)

In step 1, the composition is first applied to a substrate. The coating method is not particularly limited, and examples thereof include a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.

If necessary, the composition applied to the substrate may be dried after the application. The solvent can be removed from the coated composition by performing a drying treatment.

The thickness of the composition (composition layer) applied to the substrate is not particularly limited, but is preferably 5 to 2000. mu.m, more preferably 10 to 1000. mu.m, and still more preferably 20 to 1000. mu.m.

< step 2>

The step 2 is a step of aligning the liquid crystal compound (main agent and curing agent) contained in the composition layer obtained through the step 1 to bring the liquid crystal compound into a liquid crystal phase state. The heat conductive material in which the nematic liquid crystal phase is fixed can be obtained in step 2.

As a method for orienting the main agent and the curing agent, a method of heating the composition layer can be mentioned. Specifically, the composition (composition layer) applied to the substrate is heated to align the main agent and the curing agent in the composition layer and bring them into a liquid crystal phase.

The heating temperature of the composition layer is not particularly limited as long as the curing agent and the main agent each exhibit liquid crystallinity (preferably nematic liquid crystallinity) and the temperature is 150 ℃. In addition, when the heating temperature of the composition layer is 150 ℃ or lower, the curing reaction of the curing agent and the main agent is not substantially carried out. The heating time is, for example, 30 minutes to 12 hours.

In addition, from the viewpoint of more excellent thermal conductivity of the heat conductive material, the difference between the heating temperature in step 2 and the heating temperature in step 3 (heating temperature for main curing) described later { (heating temperature in step 3 (heating temperature for main curing)) - (heating temperature in step 2) } is preferably 10 to 150 ℃, more preferably 20 to 120 ℃, and further preferably 20 to 100 ℃.

From the viewpoint of more excellent thermal conductivity of the heat conductive material, the heating temperature in step 2 and the temperature { (temperature at which the curing reaction of the curing agent and the main agent actually starts in step 3) - (heating temperature in step 2) } at which the curing reaction of the curing agent and the main agent actually starts in step 3 described later are preferably 10 to 150 ℃, more preferably 20 to 120 ℃, and further preferably 20 to 100 ℃. When the step 3 includes a semi-curing reaction, the heating temperature in the semi-curing reaction corresponds to the temperature at which the curing reaction of the curing agent and the main agent actually starts in the step 3.

< step 3>

Step 3 is a step of curing the composition layer by reacting the curing agent with the main agent. In addition, the curing reaction is preferably performed on the composition in a sheet form. At this time, press working may be performed.

The curing reaction may be a semi-curing reaction. That is, the resulting cured product may be in a so-called B-stage state (semi-cured state).

After the semi-cured product is placed in contact with a device or the like, the layer containing the heat conductive material as the cured product is further heated and cured, whereby the adhesiveness between the layer containing the heat conductive material as the cured product and the device is further improved.

The curing method is not particularly limited, and an optimum method can be appropriately selected depending on the kinds of the active hydrogen-containing functional group contained in the curing agent and the reactive group contained in the main agent. The curing method may be, for example, a thermal curing reaction or a photo curing reaction, and the thermal curing reaction is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.

The heating temperature during the thermal curing reaction is not particularly limited, and is, for example, preferably in the range of 150 to 250 ℃, and more preferably 150 to 200 ℃. Further, when the thermosetting reaction is performed, heat treatment at different temperatures may be performed a plurality of times.

Further, when the photo-curing reaction is performed, a radical polymerization reaction by ultraviolet irradiation is more preferable.

A light source such as an ultraviolet lamp is used for ultraviolet irradiation.

The energy of the ultraviolet ray irradiation is not particularly limited, but is preferably 0.1 to 0.8J/cm in general²Left and right. The time for irradiating ultraviolet rays is not particularly limited, and may be appropriately determined from the viewpoint of both sufficient strength and productivity of the obtained layer.

[ use ]

The composition can be used as a heat conduction material in various fields. The shape of the heat conductive material is not particularly limited, and may be, for example, a sheet shape.

The heat conductive material will be described in detail below.

(Heat conductive material)

The thermally conductive material can be formed using the above composition. That is, the above composition can be used to form a thermally conductive material.

The heat conductive material is a material having excellent heat conductivity, and can be used as a heat dissipation material for a heat sink or the like. For example, the present invention can be used for heat dissipation of various devices such as power semiconductor devices. More specifically, a device with a heat conductive layer is manufactured by disposing a heat conductive layer containing the heat conductive material on the device, and heat generated from the device can be efficiently dissipated from the heat conductive layer.

The shape of the heat conductive material is not particularly limited, and may be formed into various shapes according to the use. Typically, the thermally conductive material is preferably in the form of a sheet.

The heat conductive material may be in a completely cured state or in a semi-cured state (the B-stage state). As described above, since the heat-generating material has sufficient thermal conductivity even in a semi-cured state, the heat-generating material can be used as a heat-generating material disposed in a place where light for photocuring is difficult to reach, such as a gap between components of various devices. And, it can also be used as a binder having thermal conductivity.

The thermally conductive material described above may be used in combination with other components. Specifically, for example, when the heat conductive material is in the form of a sheet, the heat conductive material in the form of a sheet may be stacked on a sheet-like support. When the above heat conductive material in a sheet form is laminated, a substrate used in the production (substrate used in step 1) can be used as it is as a sheet.