Heat conductive material, device with heat conductive layer, composition for forming heat conductive material, liquid crystal discotic compound
阅读说明：本技术 导热材料、带导热层的器件、导热材料形成用组合物、液晶性圆盘状化合物 (Heat conductive material, device with heat conductive layer, composition for forming heat conductive material, liquid crystal discotic compound ) 是由 人见诚一 高桥庆太 新居辉树 吉田有次 于 2018-07-12 设计创作，主要内容包括：本发明提供一种导热性优异的导热材料。并且,提供一种具有包含上述导热材料的导热层的带导热层的器件及用于形成上述导热材料所使用的导热材料形成用组合物。本发明的导热材料包含具有1个以上的反应性官能团的圆盘状化合物与具有与上述反应性官能团进行反应的基团的交联性化合物的固化物,所述反应性官能团选自包括羟基、羧酸基、羧酸酐基、氨基、氰酸酯基及硫醇基的组。(The invention provides a heat conductive material with excellent heat conductivity. Also provided are a thermally conductive layer-equipped device having a thermally conductive layer comprising the thermally conductive material, and a thermally conductive material-forming composition used for forming the thermally conductive material. The heat conductive material of the present invention comprises a cured product of a discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group and a thiol group, and a crosslinkable compound having a group that reacts with the reactive functional groups.)
1. A thermally conductive material, comprising: a cured product of a disk-shaped compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid anhydride group, an amino group, a cyanate group, and a thiol group, and a crosslinkable compound having a group that reacts with the reactive functional groups.
2. The thermally conductive material of claim 1,
the discotic compound is represented by the following formula (1),
[ chemical formula 1]
In the above formula, M represents nc1A disk-shaped core of valence;
Lc1represents a 2-valent linking group;
q represents a hydrogen atom or a substituent;
nc1represents an integer of 3 or more;
wherein 1 or more Q represents the reactive functional group.
3. The thermally conductive material of claim 2,
the discotic compound is a compound represented by the formula (D4),
[ chemical formula 2]
L independently represents a 2-valent linking group;
q each independently represents a hydrogen atom or a substituent;
wherein 1 or more Q represents the reactive functional group.
4. The thermally conductive material of any of claims 1-3,
the discotic compound has 3 to 6 of the reactive functional groups.
5. The thermally conductive material of any of claims 1-4,
the discotic compound has 3 to 6 groups selected from the group consisting of a hydroxyl group, a carboxylic acid group and a carboxylic anhydride group.
6. The thermally conductive material of any of claims 1-5,
the crosslinkable compound is an epoxy compound.
7. The thermally conductive material of claim 6,
the epoxy compound is a compound represented by formula (E1) or a discotic compound having an epoxy group,
[ chemical formula 3]
In the formula (E1), LE1Each independently represents a single bond or a 2-valent linking group;
LE2each independently represents a single bond, -CH-, -C (═ O) -O-, -O-C (═ O) -, -C (-CH)3)＝CH-、-CH＝C(-CH3)-、-CH＝N-、-N＝CH-、-N＝N-、-C≡C-、-N＝N+(-O-)-、-N+(-O-)＝N-、-CH＝N+(-O-)-、-N+(-O-) CH-, -CH-C (O) -, -C (O) -CH-, -CH-C (CN) -or-C (CN) -CH;
LE3an aromatic ring group having a 5-or 6-membered ring, a non-aromatic ring group having a 5-or 6-membered ring, or a polycyclic group composed of these rings, the aromatic ring group, the non-aromatic ring group, and the polycyclic group having or not having a substituent;
pe represents an integer of 0 or more;
when pe is an integer of 2 or more, (-L) is present in 2 or moreE3-LE2-) may be the same or different, respectively;
LE4each independently represents a substituent;
le independently represents an integer of 0 to 4;
when le is an integer of 2 or more, 2 or more of L are presentE4Each may be the same or different.
8. The thermally conductive material of any of claims 1-7, further comprising an inorganic.
9. The thermally conductive material of claim 8,
the inorganic matter is inorganic nitride or inorganic oxide.
10. The thermally conductive material of claim 8 or 9,
the inorganic substance is boron nitride.
11. The thermally conductive material of any one of claims 1 to 10, which is in the form of a sheet.
12. A thermally conductive device, comprising: a device and a thermally conductive layer disposed on the device and comprising the thermally conductive material of any of claims 1-11.
13. A composition for forming a thermally conductive material, comprising: a discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group, and a thiol group; and a crosslinkable compound having a group reactive with the reactive functional group.
14. The composition for forming a thermally conductive material according to claim 13, comprising: a liquid crystalline discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group and a thiol group; and a crosslinkable compound having a group reactive with the reactive functional group,
and the composition for forming a heat conductive material exhibits liquid crystallinity.
15. A liquid crystal discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group and a thiol group.
16. The liquid crystalline discotic compound according to claim 15, which is represented by the following formula (1A),
[ chemical formula 4]
In the above formula, M represents nc1A disk-shaped core of valence;
Lc11represents a 2-valent linking group;
q represents a hydrogen atom or a substituent;
nc1represents an integer of 3 or more;
wherein 1 or more Q represents the reactive functional group; and, when said M is a triphenylene skeleton, Lc11Is expressed as containingc1-alkylene-Xc1-*c2、*c1-Xc1-alkylene-)c2Orc1-Xc1-arylene-O-)c2Valency 2 of the partial structure shownA linking group;
Xc1represents-O-C (═ O) -or-C (═ O) -O-;
*c1indicating a bonding position with the disc-shaped core; *c2Indicating another bonding location.
17. The liquid crystal discotic compound according to claim 15 or 16, which is a compound represented by formula (D4A) or a compound represented by formula (D16),
[ chemical formula 5]
L11Is expressed as containingc1-alkylene-Xc1-*c2、*c1-Xc1-alkylene-)c2Orc1-Xc1-arylene-O-)c2A 2-valent linking group of the partial structure represented;
Xc1represents-O-C (═ O) -or-C (═ O) -O-;
*c1indicating a bonding position with the disc-shaped core; *c2Represents another bonding position;
q each independently represents a hydrogen atom or a substituent;
wherein 1 or more Q represents the reactive functional group;
[ chemical formula 6]
In the formula (D16), A2X、A3XAnd A4XEach independently represents-CH or-N;
R17X、R18Xand R19XIndependently represent X-X211X-(Z21X-X212X)n21X-L21X-Q; denotes the bonding position to the central ring;
X211Xand X212XEach independently represents a single bond, -O-, -C (═ O) -, or,-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-;
Z21Xeach 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;
L21Xrepresents a single bond or a 2-valent linking group;
q each independently represents a hydrogen atom or a substituent;
wherein 1 or more Q represents the reactive functional group;
n21X represents an integer of 0 to 3; when n21X is 2 or more, (Z) is present in 2 or more21X-X212X) May be the same or different.
18. The liquid crystal discotic compound according to any one of claims 15 to 17, wherein,
the reactive functional group is a group selected from the group consisting of a hydroxyl group, a carboxylic acid group and a carboxylic anhydride group.
19. The liquid crystal discotic compound according to any one of claims 15 to 18, wherein,
the phase transition temperature from the crystal phase to the liquid crystal phase is 180 ℃ or less.
Technical Field
The present invention relates to a heat conductive material, a device with a heat conductive layer, a composition for forming a heat conductive material, and a liquid crystal discotic compound.
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 progressing. With miniaturization, it is difficult to control the amount of heat generated from a power semiconductor device with higher density.
In order to cope with such a problem, a heat conductive material that promotes heat dissipation from the power semiconductor device is used (patent documents 1 and 2).
Prior art documents
Patent document
Patent document 1: japanese patent laid-open publication No. 11-323162
Patent document 2: japanese patent No. 4118691
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have studied the techniques disclosed in patent documents 1 and 2, and as a result, have found that the thermal conductivity of the disclosed heat conductive material does not necessarily reach a required level.
Accordingly, an object of the present invention is to provide a heat conductive material having excellent heat conductivity.
Another object of the present invention is to provide a thermally conductive layer-attached device having a thermally conductive layer containing the thermally conductive material, and a thermally conductive material-forming composition used for forming the thermally conductive material.
Another object of the present invention is to provide a novel liquid crystalline discotic compound.
As a result of intensive studies, the present inventors have found that the above problems can be solved by using a discotic compound having a predetermined group, and have completed the present invention.
That is, it has been found that the above object can be achieved by the following configuration.
[ 1] A heat conductive material comprising a cured product of a disk-shaped compound having 1 or more reactive functional groups and a crosslinkable compound having a group that reacts with the reactive functional groups, wherein the reactive functional groups are selected from the group consisting of hydroxyl groups, carboxylic acid anhydride groups, amino groups, cyanate groups, and thiol groups.
[ 2] the heat conductive material according to [ 1], wherein the discotic compound is represented by formula (1) described later.
[ 3] the thermally conductive material according to [ 2], wherein the discotic compound is a compound represented by formula (D4) described later.
The heat conductive material according to any one of [ 1] to [ 3], wherein the discotic compound has 3 to 6 of the reactive functional groups.
The thermally conductive material according to any one of [ 1] to [ 4], wherein the discotic compound has 3 to 6 groups selected from the group consisting of a hydroxyl group, a carboxylic acid group and a carboxylic anhydride group.
[ 6] the heat conductive material according to any one of [ 1] to [ 5], wherein the crosslinkable compound is an epoxy compound.
[ 7] the thermally conductive material according to [ 6], wherein the epoxy compound is a compound represented by formula (E1) or a discotic compound having an epoxy group.
[ 8] the heat conductive material according to any one of [ 1] to [ 7], further comprising an inorganic substance.
The heat conductive material according to [ 9] or [ 8], wherein the inorganic substance is an inorganic nitride or an inorganic oxide.
[ 10] the heat conductive material according to [ 8] or [ 9], wherein the inorganic substance is boron nitride.
[ 11] the heat conductive material according to any one of [ 1] to [ 10], which is in a sheet form.
[ 12] A thermally conductive device comprising a device and a thermally conductive layer disposed on the device and containing the thermally conductive material according to any one of [ 1] to [ 11 ].
[ 13] A composition for forming a heat conductive material, comprising: a discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group, and a thiol group; and a crosslinkable compound having a group reactive with the reactive functional group.
[ 14] the composition for forming a heat conductive material according to [ 13], which comprises: a liquid crystalline discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group and a thiol group; and a crosslinkable compound having a group reactive with the reactive functional group,
and exhibits liquid crystallinity.
[ 15] A liquid crystal discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid anhydride group, an amino group, a cyanate group and a thiol group.
The liquid crystalline discotic compound according to [ 15], which is represented by the formula (1A) described later.
[ 17] the liquid crystalline discotic compound according to [ 15] or [ 16], which is a compound represented by the formula (D4A) described later or a compound represented by the formula (D16) described later.
The liquid crystalline discotic compound according to any one of [ 15] to [ 17], wherein the reactive functional group is a group selected from the group consisting of a hydroxyl group, a carboxylic acid group and a carboxylic anhydride group.
The liquid crystalline discotic compound according to any one of [ 15] to [ 18], wherein a phase transition temperature from a crystal phase to a liquid crystal phase is 180 ℃ or lower.
Effects of the invention
According to the present invention, a heat conductive material having excellent heat conductivity can be provided.
Further, according to the present invention, it is possible to provide a thermally conductive layer-attached device having a thermally conductive layer containing the thermally conductive material and a composition for forming a thermally conductive material used for forming the thermally conductive material.
Further, according to the present invention, a novel liquid crystalline discotic compound can be provided.
Detailed Description
The heat conductive material, the device with a heat conductive layer, the composition for forming a heat conductive material (hereinafter, also simply referred to as "the present composition") and the liquid crystal discotic compound 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 numerical values before and after the term "to" as a lower limit value and an upper limit value.
In the present specification, the expression "(meth) acryloyl group" means "either or both of an acryloyl group and a methacryloyl group".
In the present specification, the expression "(meth) acrylamide group" means "either 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 atoms (-F, -Br, -Cl, -I), hydroxyl groups, amino groups, carboxylic acid groups and conjugated bases thereof, carboxylic anhydride groups, cyanate groups, unsaturated polymerizable groups, oxirane groups, oxetanyl groups, aziridinyl groups, thiol groups, isocyanate groups, thioisocyanate groups, aldehyde groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, N-alkylamino groups, N-dialkylamino groups, N-arylamino groups, N-diarylamino groups, N-alkyl-N-arylamino groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N-dialkylcarbamoyloxy groups, N-diarylcarbamoyloxy groups, N-alkyl-N-arylcarbamoyloxy groups, carboxylic anhydride groups, cyanate groups, isocyanate groups, unsaturated polymerizable groups, oxirane groups, oxetanyl groups, aziridinyl groups, alkylsulfoxy (sulfo phenoxy) radicals, arylsulfoxy radicals, acylthio radicals, acylamino radicals, N-alkylamido radicals, N-arylacylamino radicals, ureido radicals, N ' -alkylureido radicals, N ' -dialkylureido radicals, N ' -arylureido radicals, N ' -diarylureido radicals, N ' -alkyl-N ' -arylureido radicals, N-alkylureido radicals, N-arylureido radicals, N ' -alkyl-N-alkylureido radicals, N ' -alkyl-N-arylureido radicals, N ' -dialkyl-N-alkylureido radicals, N ' -dialkyl-N-arylureido radicals, N ' -aryl-N-alkylureido radicals, N ' -aryl-N-arylureido radicals, N ', n ' -diaryl-N-alkylureido, 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 ' -arylureido, N ' -alkyl-N ' -aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO)3H) And conjugate bases thereof, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylaminoSulfinyl, sulfamoyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-acylsulfamoyl and conjugate base thereof, N-alkylsulfonylsulfamoyl (-SO)2NHSO2(alKyl)) and its conjugated base, N-arylsulfonylsulfamoyl (-SO)2NHSO2(aryl)) and a conjugated base thereof, an N-alkylsulfonylcarbamoyl group (-CONHSO)2(alKyl)) and its conjugate base, N-arylsulfonylcarbamoyl (-CONHSO)2(aryl)) and a conjugated base thereof, an alkoxysilyl group (-Si (Oakyl))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 conjugated 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 a substituted group, if possible.
Examples of the unsaturated polymerizable group include a (meth) acryloyl group, a (meth) acrylamide group, and substituents represented by the following Q1 to Q7.
[ chemical formula 1]
[ Heat-conducting Material ]
The heat conductive material of the present invention contains a cured product of a discotic compound having 1 or more reactive functional groups (hereinafter, also referred to as a "specific discotic compound") selected from the group consisting of a hydroxyl group, a carboxylic acid anhydride group, an amino group, a cyanate group, and a thiol group, and a crosslinkable compound having a group that reacts with the reactive functional groups (hereinafter, also referred to as a "crosslinkable compound"). That is, the heat conductive material of the present invention contains a cured product obtained by reacting a specific discotic compound with a crosslinkable compound.
The present inventors have found that the thermal conductivity of a thermally conductive material can be improved by using a specific discotic compound and a crosslinkable compound.
The mechanism is not necessarily clear, but it is considered that the rod-like compound described in patent documents 1 and 2 can conduct heat only linearly (one-dimensionally), whereas the cured product of a specific disk-like compound can conduct heat in the normal direction with respect to the disk-like structure thereof, and therefore the heat conduction path is increased and the heat conductivity is improved.
First, specific disk-shaped compounds and crosslinkable compounds used for obtaining a cured product contained in a heat conductive material will be described in detail below.
[ specific discotic Compound ]
Specific disk-shaped compounds can be cited as the raw material of the cured product contained in the heat conductive material.
In the present specification, a discotic compound means a compound having a discotic structure at least partially. The disk-shaped compound can form a stacked (stacking) structure to be a columnar structure by the disk-shaped structure. The discotic compound preferably has at least an aromatic ring and is capable of forming a stacking structure based on pi-pi interaction between molecules to have a columnar structure.
Such columnar structure is considered to promote heat conduction in the normal direction with respect to the disk-shaped structure as described above, and to contribute to improvement in heat conductivity.
The specific discotic compound has 1 or more selected from hydroxylGroup (-OH), carboxylic acid group (-COOH), carboxylic anhydride group, amino group (-NH)2) A cyanate group (-O-C ≡ N) and a thiol group (-SH).
Among these, from the viewpoint of more excellent thermal conductivity of the heat conductive material, the specific disk-shaped compound preferably has 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid anhydride group, an amino group, and a cyanate group, and more preferably 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, and a carboxylic acid anhydride group.
In addition, the specific discotic compound preferably has 3 to 8 reactive functional groups, and more preferably 3 to 6 reactive functional groups, from the viewpoint of more excellent thermal conductivity of the heat conductive material.
Among them, the reactive functional group preferably has 3 to 8 reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group and a carboxylic anhydride group, and more preferably has 3 to 6 reactive functional groups.
In addition, the cured product of a specific discotic compound having 3 or more reactive functional groups has a high glass transition temperature and exhibits excellent heat resistance.
The hydroxyl group is preferably a hydroxyl group directly bonded to an aromatic ring such as a phenyl group.
The carboxylic anhydride group is a 1-valent substituent obtained by removing an arbitrary hydrogen atom from an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, or the like.
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 from the viewpoint of more excellent thermal conductivity of the heat conductive material (particularly, from the viewpoint of more excellent thermal conductivity when the heat conductive material is formed into a thicker film (for example, 400 μm or more). That is, the discotic compound is preferably a liquid crystalline discotic compound.
It is presumed that a plurality of domains (domains) corresponding to the degree of orientation order are formed in the cured product of the specific discotic compound and the crosslinkable compound, and that boundaries (grain boundaries) between the plurality of domains exist. It is considered that when the specific discotic compound is a liquid crystalline discotic compound, the domain size can be further increased (in other words, the number of grain boundaries can be further reduced), and as a result, the thermal conductivity of the cured product is further improved particularly when the cured product is made thick.
The liquid crystallinity of a specific discotic compound can be confirmed by polarization microscope observation or differential scanning calorimetry.
Specific examples of the discotic compound include c.destrand et al, mol.crysr.liq.cryst, vol.71, page 111 (1981); edited by the society of chemical Japan, the general term of journal chemistry, No.22, liquid Crystal chemistry, Chapter 5, Chapter 10, section 2 (1994); b.kohne et al, angelw.chem.soc.chem.comm., page1794 (1985); j.zhang et 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 angelw. 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.
Specific examples of the discotic compound include compounds represented by the following formula (1).
[ chemical formula 2]
In the above formula, M represents nc1A disk-shaped core of valence.
Lc1Represents a 2-valent linking group.
Q represents a hydrogen atom or a substituent.
nc1Represents an integer of 3 or more.
Wherein 1 or more Q's represent the above reactive functional group.
The disk-shaped core portion denoted by M is not particularly limited, and may be, for example, the structures denoted by formulas (CR1) to (CR 16). Is represented by the formulac1-bonding position of group represented by Q. In addition, (CR16), A2X、A3XAnd A4XEach independently represents-CH or N, preferably a2X、A3XAnd A4XAll represent-CH ═ c.
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
Lc1Represents a 2-valent linking group.
L is a heat conductive material having more excellent thermal conductivityc1Each independently preferably selected from the group consisting of alkylene, alkenylene, arylene, heteroarylene, -C (═ O) -, -NRc1More preferably, the group selected from the group consisting of-O-, -S-, and combinations thereof, will be selected from the group consisting of alkylene, alkenylene, arylene, heteroarylene, -C (═ O) -, -NRc1A combination of 2 or more of the groups-O-and-S-.
R is as defined abovec1Represents a hydrogen atom or an alkyl group. Rc1The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 3.
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, and more preferably 6.
The number of carbon atoms of the heteroarylene group is preferably 6 or less. The heteroarylene group is preferably a 5-or 6-membered ring. The hetero atom contained in the heteroarylene group is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, and the like. In addition, the number of hetero atoms in the heteroarylene group is not particularly limited, and is, for example, 1 to 3.
The alkylene group, alkenylene group, arylene group, and heteroarylene group may have a substituent (preferably, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an acyloxy group, or the like).
When M is a triphenylene skeleton represented by the formula (CR4), L is preferably L from the viewpoint that the discotic compound exhibits liquid crystallinity and the heat conductive material has more excellent heat conductivityc1Is expressed as containingc1-alkylene-Xc1-*c2、*c1-Xc1-alkylene-)c2Orc1-Xc1-arylene-O-)c2The 2-valent linking group of the partial structure shown.
Xc1represents-O-C (═ O) -or-C (═ O) -O-.
*c1Indicating the bonding position with the disc-shaped core. *c2Indicating another bonding location.
Q each independently represents a hydrogen atom or a substituent.
Examples of the substituent include those exemplified in the above substituent group Y. More specifically, examples of the substituent include the above-mentioned reactive functional group, halogen atom, isocyanate group, cyano group, unsaturated polymerizable group, oxirane group, oxetanyl group, aziridine group, thioisocyanate group, aldehyde group, and sulfonic acid group.
In the formula (1), 1 or more of Q's represent a reactive functional group. Among these, from the viewpoint of further improving the thermal conductivity of the heat conductive material, it is preferable that all Q represent a reactive functional group.
nc1Represents an integer of 3 or more. From the viewpoint of more excellent thermal conductivity of the heat conductive material, the heat conductive material is excellent3 to 8 is selected, and 3 to 6 is more preferable.
As the specific discotic compound, a compound represented by any one of the formulae (D1) to (D16) shown below is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.
In the following formulae, "-LQ" represents "-L-Q" and "QL-" represents "Q-L-".
First, the formulae (D1) to (D15) will be described in detail.
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
[ chemical formula 11]
In the formulae (D1) to (D15), L represents a 2-valent linking group.
The 2-valent linking group represented by L has the same meaning as that of L in the above formula (1)c1The 2-valent linking groups are the same, and the preferred modes are also the same.
Among these, L is preferably a group selected from the group consisting of alkylene, alkenylene, arylene, -C (═ O) -, -NH-, -O-, -S-, and a combination thereof, and more preferably a group obtained by combining 2 or more groups selected from the group consisting of alkylene, alkenylene, arylene, -C (═ O) -, -NH-, -O-, and-S-, from the viewpoint of more excellent thermal conductivity of the heat conductive material.
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, alkenylene group and arylene group may have a substituent (preferably, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an acyloxy group or the like).
Examples of L are shown below. In the following examples, the left side connecting bond is bonded to the central structure (hereinafter, also simply referred to as "central ring") of the compound represented by any one of formulae (D1) to (D15), and the right side connecting bond is bonded to Q.
AL means alkylene or alkenylene and AR means arylene.
In the compound represented by formula (D4), L preferably represents a group containing x from the viewpoint that the discotic compound exhibits liquid crystallinity and the heat conductive material has more excellent heat conductivity1-alkylene-O-C (═ O) -) and2、*1-alkylene-C (═ O) -O —)2、*1-O-C (═ O) -alkylene- >2、*1-C (═ O) -O-alkylene- >2、*1-C (═ O) -O-arylene-O- >2Or1-O-C (═ O) -arylene-O- >2The 2-valent linking group of the partial structure shown. *1Indicating the bonding position with the center ring. *2Indicating another bonding location. In addition, a2The other bonding position is a bonding position to another atom in L or a bonding position to Q.
For example, L101 described below belongs to the group consisting of1-alkylene-C (═ O) -O —)2The 2-valent linking group of the partial structure shown.
L101：-AL-C(＝O)-O-AL-
L102：-AL-C(＝O)-O-AL-O-
L103：-AL-C(＝O)-O-AL-O-AL-
L104：-AL-C(＝O)-O-AL-O-C(＝O)-
L105：-C(＝O)-AR-O-AL-
L106：-C(＝O)-AR-O-AL-O-
L107：-C(＝O)-AR-O-AL-O-C(＝O)-
L108：-C(＝O)-NH-AL-
L109：-NH-AL-O-
L110：-NH-AL-O-C(＝O)-
L111：-O-AL-
L112：-O-AL-O-
L113：-O-AL-O-C(＝O)-
L114：-O-AL-O-C(＝O)-NH-AL-
L115：-O-AL-S-AL-
L116：-O-C(＝O)-AL-AR-O-AL-O-C(＝O)-
L117：-O-C(＝O)-AR-O-AL-C(＝O)-
L118：-O-C(＝O)-AR-O-AL-O-C(＝O)-
L119：-O-C(＝O)-AR-O-AL-O-AL-O-C(＝O)-
L120：-O-C(＝O)-AR-O-AL-O-AL-O-AL-O-C(＝O)-
L121：-S-AL-
L122：-S-AL-O-
L123：-S-AL-O-C(＝O)-
L124：-S-AL-S-AL-
L125：-S-AR-AL-
L126：-O-C(＝O)-AL-
L127：-O-C(＝O)-AL-O-
L128：-O-C(＝O)-AR-O-AL-
L129：-O-C(＝O)-
L130：-O-C(＝O)-AR-O-AL-O-C(＝O)-AL-S-AR-
L131：-O-C(＝O)-AL-S-AR-
L132：-O-C(＝O)-AR-O-AL-O-C(＝O)-AL-S-AL-
L133：-O-C(＝O)-AL-S-AR-
L134：-O-AL-S-AR-
L135：-AL-C(＝O)-O-AL-O-C(＝O)-AL-S-AR-
L136：-AL-C(＝O)-O-AL-O-C(＝O)-AL-S-AL-
L137：-O-AL-O-AR-
L138：-O-AL-O-C(＝O)-AR-
L139：-O-AL-NH-AR-
L140：-O-C(＝O)-AL-O-AR-
L141：-O-C(＝O)-AR-O-AL-O-AR-
L142：-AL-C(＝O)-O-AR-
L143：-AL-C(＝O)-O-AL-O-AR-
In the formulae (D1) to (D15), Q represents a hydrogen atom or a substituent. In addition, Q is as described above. Wherein 1 or more Q's represent the above reactive functional group. Among these, from the viewpoint of further improving the thermal conductivity of the heat conductive material, it is preferable that all Q represent a reactive functional group.
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 conductive material has more excellent heat conductivity. In other words, the central ring of the specific discotic compound is preferably a triphenylene ring.
The compound represented by the formula (D4) is preferably a compound represented by the formula (XI) from the viewpoint that the heat conductive material is more excellent in heat conductivity.
[ chemical formula 12]
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-P11。
More preferably R11、R12、R13、R14、R15And R16All are X-X11-L11-P11. Furthermore, 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 of which 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 2-valent linking group include a group consisting of-O-, -OC (-O) -, -C (-O) O-, -S-, -NH-, an alkylene group (having preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 7 carbon atoms), an arylene group (having preferably 6 to 20, more preferably 6 to 14, further preferably 6 to 10 carbon atoms), or a combination thereof.
Examples of the alkylene group include a methylene group, a vinyl group, a propenyl 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 and an 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 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, it is preferable that the alkylene group is unsubstituted.
as-X11-L11Examples of (D) include L101 to L143 as examples of L.
Further, from the viewpoint that the discotic compound exhibits liquid crystallinity and the heat conductive material is more excellent in heat conductivity, -X11-L11-preferably means comprising1-O-C (═ O) -alkylene- >2、*1-C (═ O) -O-alkylene- >2、*1-C (═ O) -O-arylene-O- >2Or1-O-C (═ O) -arylene-O- >2The 2-valent linking group of the partial structure shown. *1Represents a bonding position to a triphenylene ring. *2Indicating another bonding location. In addition, a2The other bonding position indicated is intended to indicate the bond with L11Or represents a bonding position with P11The bonding position of (2).
P11Each independently represents a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group or a cyanate group. Among them, P is preferable from the viewpoint of more excellent thermal conductivity11Each independently preferably a hydroxyl group, a carboxylic acid group or a carboxylic anhydride group.
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.
X12And X11Similarly, the preferred conditions are also the same.
L12And L11Similarly, the preferred conditions are also the same.
as-X12-L12Examples of (D) include L101 to L143 as examples of L.
Further, from the viewpoint that the discotic compound exhibits liquid crystallinity and the heat conductive material is more excellent in heat conductivity, -X12-L12-preferably means comprising1-O-C (═ O) -alkylene- >2、*1-C (═ O) -O-alkylene- >2、*1-C (═ O) -O-arylene-O- >2Or1-O-C (═ O) -arylene-O- >2The 2-valent linking group of the partial structure shown. *1Represents a bonding position to a triphenylene ring. *2Represents anotherA bonding position. In addition, a2The other bonding position indicated is intended to indicate the bond with L12Or a bonding position to the other atom in (1) or with Y12The bonding position of (2).
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.
Y12The alkyl group is preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an ethylene oxide group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, or an ethylene oxide group or a propylene oxide group having 1 to 20 carbon atoms.
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 Japanese Yamazenicorporation, 12 years).
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, the compound represented by the formula (D16) will be described in detail.
[ chemical formula 13]
In the formula (D16), A2X、A3XAnd A4XEach independently represents-CH or-N. Wherein A is2X、A3XAnd A4XEach is independently preferably-CH ═ CH.
R17X、R18XAnd R19XIndependently represent X-X211X-(Z21X-X212X)n21X-L21X-Q. Denotes the bonding site to the central ring.
X211XAnd X212XEach 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-.
Z21XEach 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.
L21XRepresents a single bond or a 2-valent linking group.
Q has the same meaning as Q in the formulae (D1) to (D15), and preferable conditions are also the same. That is, at least 1Q of Q's in the plural number represents a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group or a cyanate group.
n21X represents an integer of 0 to 3. When n21X is 2 or more, (Z) is present in 2 or more21X-X212X) May be the same or different.
The compound represented by the formula (D16) is preferably a compound represented by the formula (XII).
[ chemical formula 14]
In the formula (XII), A2、A3And A4Each independently represents-CH or-N. Wherein A is2、A3And A4Preferably, -CH ═ CH.In other words, the central ring of the specific discotic compound is also preferably a benzene ring.
R17、R18And R19Independently represent X-X211-(Z21-X212)n21-L21-P21or-X221-(Z22-X222)n22-Y22. Denotes the bonding site to the central ring.
R17、R18And R19More than 2 of the total number of the amino acids are-X211-(Z21-X212)n21-L21-P21. From the viewpoint of more excellent thermal conductivity of the heat conductive material, R is preferable17、R18And R19All are X-X211-(Z21-X212)n21-L21-P21。
Moreover, R is preferred17、R18And R19All the same.
X211、X212、X221And X222Each 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 X211、X212、X221And X222Each 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 and an aromatic heterocyclic group.
The aromatic ring group and the non-aromatic ring group may have a substituent. The number of substituents is preferably 1 or 2, more preferably 1. The substitution position of the substituent is not particularly limited. As the substituent, a halogen atom or a methyl group is preferable. It is also preferable that the aromatic ring group and the non-aromatic ring group are unsubstituted.
Examples of the aromatic heterocyclic group include the following aromatic heterocyclic groups.
[ chemical formula 15]
Wherein represents a bond to X211Or X221The location of (1). Denotes a bond to X212Or X222The location of (1). 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 both are nitrogen atoms. And, X4Preferably an oxygen atom.
When n21 and n22 described later are 2 or more, (Z) is present in 2 or more21-X212) And (Z)22-X222) Each may be the same or different.
L21Each independently represents a single bond or a 2-valent linking group, and has the meaning of L in the formula (XI)11The same is true. As L21Preferably, the group is one of-O-, -OC (-O) -, -C (-O) O-, -S-, -NH-, alkylene (preferably having 1 to 10, more preferably 1 to 8, and even more preferably 1 to 7 carbon atoms), arylene (preferably having 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10 carbon atoms), or a combination thereof.
When n22 described later is 1 or more, it is designated as-X212-L21Examples of (D) include L101 to L143 which are examples of L in the above formulae (D1) to (D15).
P21Each independently represents a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group or a cyanate group. Among these, P is a thermally conductive material having more excellent thermal conductivity21Each independently preferably a hydroxyl group, a carboxylic acid group, or a carboxylic anhydride group.
Y22Each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a C1 to E20 in the linear, branched or cyclic alkyl group, 1 or 2 or more methylene groups are replaced by-O-, -S-, -NH-, -N (CH)3) a-C (═ O) -, -OC (═ O) -, or-C (═ O) O-substituted radical, the meaning of which is as defined for Y in formula (XI)12Similarly, the preferred ranges are also the same.
n21 and n22 each independently represent an integer of 0 to 3, and are preferably integers 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-X212-L21-P21。
[ chemical formula 16]
For details and specific examples of the compound represented by the formula (XII), reference can be made to 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 specific discotic compound is preferably a compound having a hydrogen-bonding functional group from the viewpoint that stacking is enhanced by decreasing the electron density to thereby make it easy to form columnar aggregates. 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-.
The specific discotic compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
[ crosslinkable Compound ]
The crosslinkable compound is a compound which reacts with the specific discotic compound.
The crosslinkable compound has a group that reacts with the reactive functional group (hereinafter, also referred to as "crosslinkable group").
Examples of the crosslinkable group include an oxirane group, an oxetanyl group, a hydroxyl group, a carboxylic acid group, a halobenzyl group, a carboxylic anhydride group, a cyanate group, an isocyanate group, an amino group, an aldehyde group, an aziridine group, and an alkoxysilyl group.
The crosslinkable group can be appropriately selected depending on the kind of the reactive functional group.
Examples of the crosslinkable group that can be used when the reactive 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 crosslinkable group that can be used when the reactive functional group is a carboxylic acid group include an oxirane group, an oxetanyl group, a halobenzyl group, a cyanate group, an amino group, an isocyanate group, and an aziridine group.
Examples of the crosslinkable group that can be used when the reactive functional group is a carboxylic anhydride group include an oxirane group, an oxetanyl group, and a hydroxyl group.
Examples of the crosslinkable group that can be used when the reactive functional group is an amino group include an oxirane group, an oxetanyl group, a carboxylic acid group, a halobenzyl group, an isocyanate group, an aldehyde group, and a carbonyl group.
Examples of the crosslinkable group that can be used when the reactive functional group is a cyanate group include an ethylene oxide group, a carboxylic acid group, and an unsaturated polymerizable group.
Examples of the crosslinkable group that can be used when the reactive functional group is a thiol group include an oxirane group, an oxetanyl group, a halobenzyl group, a carboxylic anhydride group, an isocyanate group, and an alkoxysilyl group.
Among them, from the viewpoint of more excellent thermal conductivity of the heat conductive material and from the viewpoint of excellent adhesion of the heat conductive material to a device or the like, the crosslinkable group is preferably an ethylene oxide group or an oxetane group, and more preferably an ethylene oxide group.
In the present specification, an oxirane group is a functional group also referred to as an epoxy group, and may be a group containing an oxirane (ethylene oxide), and includes, for example, a group in which 2 adjacent carbon atoms of a saturated hydrocarbon ring group are bonded via an oxo group (-O-) to form an oxirane ring.
Hereinafter, a crosslinkable compound having an oxirane group (epoxy group) as a crosslinkable group is also referred to as an epoxy compound.
The number of crosslinkable groups of the crosslinkable compound is not particularly limited, but is preferably 2 to 8, more preferably 2 to 6.
Among them, the crosslinkable compound is preferably an epoxy compound.
Examples of the epoxy compound include a rod-like compound (rod-like epoxy compound) having an epoxy group and a disk-like compound (disk-like epoxy compound) having an epoxy group, which are represented by the formula (E1) described later, a bisphenol a diglycidyl ether resin, a bisphenol F diglycidyl ether resin, and the like.
The discotic compound is defined as above.
As the crosslinkable compound, an epoxy compound represented by the formula (E1) described later or a discotic epoxy compound is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.
The crosslinkable compound may or may not have liquid crystallinity, and preferably has liquid crystallinity from the viewpoint of more excellent thermal conductivity of the heat conductive material.
The rod-shaped epoxy compound and the disk-shaped epoxy compound are described in detail below.
(epoxy Compound in stick form)
When the crosslinkable compound is a rod-like epoxy compound, the number of epoxy groups in the rod-like epoxy compound is not particularly limited, but is preferably 2 to 8, more preferably 2 to 6, and further preferably 2.
Among these, the epoxy compound represented by the formula (E1) is more preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.
[ chemical formula 17]
In the formula (E1), LE1Each independently represents a single bond or a 2-valent linking group.
Wherein L isE1A 2-valent linking group is preferred.
The 2-valent linking group is preferably-O-, -S-, -C (═ O) -, -NH-, -CH ═ CH-, -C ≡ C-, -CH ═ N-, -N ═ CH-, -N ═ N-, an alkylene group which may have a substituent, or a group composed of a combination of 2 or more of them, and more preferably-O-alkylene-or-alkylene-O-.
The alkylene group may be any of linear, branched and cyclic, but is preferably a linear alkylene group having 1 to 2 carbon atoms.
LE2Each independently represents a single bond, -CH-, -C (═ O) -O-, -O-C (═ O) -, -C (-CH)3)＝CH-、-CH＝C(-CH3)-、-CH＝N-、-N＝CH-、-N＝N-、-C≡C-、-N＝N+(-O-)-、-N+(-O-)＝N-、-CH＝N+(-O-)-、-N+(-O-) CH-, -CH-C (O) -, -C (O) -CH-, -CH-C (CN) -or-C (CN) -CH-.
Wherein L isE2Each independently of the others is preferably a single bond, -C (═ O) -O-, or-O-C (═ O) -.
LE3Each independently represents a single bond, or an aromatic ring group having a 5-or 6-membered ring which may have a substituent, or a non-aromatic ring group having a 5-or 6-membered ring, or a polycyclic group composed of these rings.
As LE3Examples of the aromatic ring group and the non-aromatic ring group include optionally substituted 1, 4-cyclohexanediyl, 1, 4-cyclohexenediyl, 1, 4-phenylene, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, 1,3, 4-thiadiazole-2, 5-diyl, 1,3, 4-oxadiazole-2, 5-diyl, naphthalene-2, 6-diyl, naphthalene-1, 5-diyl, thiophene-2, 5-diyl and pyridazine-3, 6-diyl. In the case of 1, 4-cyclohexanediyl, it may be either a trans isomer or a cis isomer, or may be in any ratioThe mixtures of examples. Among them, the trans-isomer is preferred.
Wherein L isE3Preference is given to a single bond, 1, 4-phenylene or 1, 4-cyclohexenediyl.
LE3The substituents of the groups are each independently preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group or an acetyl group, and more preferably an alkyl group (preferably having 1 carbon atom).
When a plurality of substituents are present, the substituents may be the same or different.
pe represents an integer of 0 or more.
When pe is an integer of 2 or more, (-L) is present in 2 or moreE3-LE2-) may be the same or different, respectively.
Here, pe is preferably 0 to 2, and preferably 0 or 1.
LE4Each independently represents a substituent.
The substituents are each independently preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group or an acetyl group, and more preferably an alkyl group (preferably having 1 carbon atom).
When le to be described later is an integer of 2 or more, (L)E4)leL in which there are pluralE4Each may be the same or different.
le independently represents an integer of 0 to 4.
Wherein le is preferably 0 to 2 independently.
The molecular weight of the epoxy compound represented by the formula (E1) is preferably 100 to 3000, more preferably 200 to 2500, and even more preferably 250 to 2000, from the viewpoint of further excellent thermal conductivity.
Only 1 kind of the epoxy compound represented by the formula (E1) may be used, or 2 or more kinds may be used simultaneously.
(disk-shaped epoxy Compound)
The disc-shaped epoxy compound is not particularly limited as long as it is a disc-shaped compound having an epoxy group.
The disc-shaped epoxy compound preferably has 3 to 8 epoxy groups, and more preferably 3 to 6 epoxy groups, from the viewpoint of more excellent thermal conductivity of the heat conductive material.
Further, a cured product of a disc-shaped compound having 3 or more epoxy groups has a high glass transition temperature and exhibits excellent heat resistance.
Specific examples of the disk-shaped compound are not particularly limited, and examples thereof include compounds having the disk-shaped core as a partial structure.
The crosslinkable compound may be used in 1 kind alone, or 2 or more kinds may be used simultaneously.
The content of the cured product of the specific discotic compound and the crosslinkable compound in the heat conductive material of the present invention is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 15 to 80% by mass, based on the total mass of the heat conductive material of the present invention.
The cured product of the specific discotic compound and the crosslinkable compound preferably has a columnar structure. The columnar structure has high degree of order, and the thermal conductivity of the cured material is further improved by forming the columnar structure by the cured material. When a peak derived from a columnar structure can be confirmed in a range of 2 θ of 10 degrees or less by measuring a cured product by XRD (X-ray diffraction), it can be judged that the cured product forms a columnar structure.
The method for producing the cured product is not particularly limited, and examples thereof include a method in which a specific disc-shaped compound is reacted with a crosslinkable compound under heating conditions described in < method for curing composition > described later.
[ other ingredients ]
The heat conductive material of the present invention may contain other components in addition to the cured product of the specific disk-shaped compound and the crosslinkable compound.
In addition, the heat conductive material may contain an uncured specific disk-shaped compound and an uncured crosslinkable compound.
As other components, inorganic substances are typically mentioned.
< inorganic substance >
The heat conductive material of the present invention preferably contains an inorganic substance from the viewpoint that the heat conductive material is more excellent in heat conductivity.
As the inorganic substance, any inorganic substance conventionally used for inorganic fillers of heat conductive materials can be used. As the inorganic substance, an inorganic oxide or an inorganic nitride is preferable. The inorganic substance may be an inorganic nitride oxide. The shape of the inorganic substance is not particularly limited, and may be particulate, film-like or flat. Examples of the shape of the particulate inorganic material include rice grain shape, spherical shape, cubic shape, spindle shape, scaly shape, agglomerated shape, and irregular shape.
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)。
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.
The inorganic oxide may be an oxide produced by oxidizing a metal prepared in a non-oxide form under an 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) and zirconium nitride (ZrN).
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 better 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 a method for measuring the average particle size, 100 inorganic substances were randomly selected by using an electron microscope, the particle size (major axis) of each inorganic substance was measured, and the particle size and the major axis were arithmetically averaged to obtain the average particle size. In addition, when a commercially available product is used, a product catalog value may also be used.
The inorganic substances may be used alone in 1 kind or in combination of 2 or more kinds.
The content of the inorganic substance in the heat conductive material of the present invention is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, and still more preferably 40 to 90% by mass, based on the total mass of the heat conductive material of the present invention.
The heat conductive material may contain the cured product, and the production method thereof is not particularly limited, but the heat conductive material is preferably formed using a heat conductive material-forming composition (present composition) containing a specific disk-shaped compound and a crosslinkable compound. That is, the composition is preferably cured to obtain a heat conductive material containing the cured product.
The present composition and the method for producing the heat conductive material of the present invention using the present composition are explained below.
[ composition for Forming Heat conductive Material ]
The composition comprises a specific discotic compound and a crosslinkable compound.
The specific discotic compound and the crosslinkable compound are as defined above.
The content of the specific discotic compound in the present composition is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 15 to 80% by mass, based on the total solid content of the composition.
The content of the crosslinkable compound in the present composition is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 15 to 80% by mass, based on the total solid content of the composition.
The content of the crosslinkable compound in the composition is preferably an amount such that the ratio of the number of crosslinkable groups of the crosslinkable compound in the composition to the number of reactive functional groups of the specific discotic compound in the composition (the number of crosslinkable groups/the number of reactive functional groups) is 0.1 to 10.0, more preferably 0.1 to 9.0, and still more preferably 0.1 to 8.0.
The present composition may contain other components such as inorganic substances, solvents, and curing accelerators.
The definition of inorganic substance is as described above.
< solvent >
The present composition may further comprise a solvent.
The kind of the solvent is not particularly limited, and an organic solvent is preferred. Examples of the organic solvent include ethyl acetate, Methyl Ethyl Ketone (MEK), dichloromethane, and Tetrahydrofuran (THF).
The content of the solvent in the present composition is preferably an amount such that the total amount of the total solid content in the present composition (solid content concentration) is 1 to 90% by mass, more preferably 5 to 85% by mass, and still more preferably 10 to 80% by mass, based on the total mass of the present composition.
< curing Accelerator >
Examples of the curing accelerator include triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, and 1-benzyl-2-methylimidazole, and the curing accelerator described in paragraph 0052 of jp 2012-067225 a. Among them, triphenylphosphine is preferable.
The content of the curing accelerator in the present composition is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.01 to 10% by mass, based on the total solid content of the composition.
The amount of the curing accelerator used is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.01 to 10% by mass, based on the total mass of the specific discotic compound and the crosslinkable compound.
In addition, when an epoxy compound is used as the crosslinkable compound and a specific discotic compound has an amino group, it may be preferable not to use a curing accelerator. This is because the amino group is excellent in reactivity with the oxirane group (epoxy group), and therefore, it is not necessary to use a curing accelerator in some cases to further improve the reactivity.
In addition, when the present composition contains a specific discotic compound exhibiting liquid crystallinity and the composition itself exhibits liquid crystallinity, it can be preferably used as a curable composition excellent in thermal conductivity and heat resistance. That is, the present composition is also preferably in the following manner: the liquid crystal display device comprises a liquid crystal discotic compound having 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group and a thiol group, and a crosslinkable compound having a group reactive with the reactive functional groups, and exhibits liquid crystallinity.
In the case of the above embodiment, the crosslinkable compound preferably exhibits liquid crystallinity as well.
The liquid crystal discotic compound is preferably a liquid crystal discotic compound represented by the formula (1A) described later.
The crosslinkable compound is as described above.
< method for producing composition >
The method for producing the composition is not particularly limited, and a known method can be used. For example, the resin composition can be produced by mixing the above-mentioned various components (specific discotic compound, crosslinkable compound, inorganic substance, curing accelerator, solvent, and the like) by a known method. In the mixing, the respective components may be mixed together or may be mixed sequentially.
< method for curing composition >
The method for curing the present composition is not particularly limited, and an optimum method can be appropriately selected depending on the kinds of the specific discotic compound and the crosslinkable compound. The curing method is not particularly limited, but a thermal curing reaction is preferred.
The heating temperature at the time of the heat curing reaction is not particularly limited. For example, it may be appropriately selected within the range of 50 to 250 ℃. Further, when the thermosetting reaction is performed, heat treatment at different temperatures may be performed a plurality of times.
The present composition formed into a film or sheet is preferably subjected to a curing treatment. Specifically, for example, the present composition may be applied to form a film and then subjected to a curing reaction. At this time, press working may be performed.
The curing treatment may be terminated at a point of time when the present composition is made into a semi-cured state. The thermally conductive material of the present invention in a semi-cured state may be disposed so as to be in contact with a device or the like to be used, and then cured by heating or the like to be finally cured. It is also preferable that the device and the heat conductive material of the present invention are bonded by heating or the like at the time of main curing.
With regard to the production of heat-conducting materials involving curing reactions, reference can be made to "high heat-conducting composites" (CMC published by bamboo).
The shape of the heat conductive material is not particularly limited, and the heat conductive material can be molded into various shapes according to the use. Typical shapes of the molded heat conductive material include a sheet shape.
Also, the thermal conductivity of the thermally conductive material of the present invention is preferably isotropic, not anisotropic.
[ use of Heat conductive Material ]
The heat conductive material of the present invention can be used as a heat dissipating material such as a heat sink, and can be used for heat dissipating purposes of various devices. More specifically, a device with a heat conductive layer is manufactured by disposing a heat conductive layer including the heat conductive material of the present invention on the device, and heat generated from the device can be efficiently dissipated from the heat conductive layer.
The heat conductive material of the present invention has sufficient heat conductivity and high heat resistance, and is therefore suitable for heat dissipation applications of power semiconductor devices used in various electrical devices such as personal computers, general household electrical appliances, and automobiles.
The heat conductive material of the present invention has sufficient heat conductivity even in a semi-cured state, and therefore can be used as a heat dissipating material for a portion which is difficult to be reached by light curing, such as a gap between components of various devices. Further, the adhesive can also be used as an adhesive having thermal conductivity.
The thermally conductive material of the present invention may be used in combination with other components than those formed from the present composition.
For example, a sheet-like heat conductive material may be combined with a sheet-like support other than the layer formed from the present composition.
Examples of the sheet-like support 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. The metal thin film may be a copper thin film.
[ liquid Crystal discotic Compound ]
The liquid crystalline discotic compound of the present invention has 1 or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a carboxylic anhydride group, an amino group, a cyanate group and a thiol group.
The definition of the discotic compound and its preferred embodiments and the reactive functional group and its preferred embodiments are as described above.
The molecular weight of the liquid crystalline discotic compound is preferably 3000 or less, more preferably 2500 or less, from the viewpoint of thermal conductivity. The lower limit of the molecular weight is not particularly limited, and is, for example, 200 or more.
Among the liquid crystal discotic compounds, a compound represented by the formula (1A) described later is preferable from the viewpoint of further excellent thermal conductivity.
[ chemical formula 18]
In the above formula, M represents nc1A disk-shaped core of valence.
Lc11Represents a 2-valent linking group.
Q represents a hydrogen atom or a substituent.
nc1Represents an integer of 3 or more.
Wherein 1 or more Q's represent the above reactive functional group. And, when the above M is a triphenylene skeleton, Lc11Is expressed as containingc1-alkylene-Xc1-*c2、*c1-Xc1-alkylene-)c2Orc1-Xc1-arylene-O-)c2The 2-valent linking group of the partial structure shown.
Xc1represents-O-C (═ O) -or-C (═ O) -O-.
*c1Indicating the bonding position with the disc-shaped core. *c2Indicating another bonding location.
In the above formula (1A), M, nc1、Lc11And Q are as defined above in formula (1) M, nc1、Lc1And Q are the same, and the preferred embodiment is the same.
Among them, the compound represented by the formula (D4A) or the compound represented by the formula (D16) is preferable as the compound represented by the formula (1A).
[ chemical formula 19]
L11Is expressed as containingc1-alkylene-Xc1-*c2、*c1-Xc1-alkylene-)c2Orc1-Xc1-arylene-O-)c2The 2-valent linking group of the partial structure shown.
Xc1represents-O-C (═ O) -or-C (═ O) -O-.
*c1Indicating the bonding position with the disc-shaped core. *c2Indicating another bonding location.
Q each independently represents a hydrogen atom or a substituent.
Wherein 1 or more Q's represent the above reactive functional group.
In the formula (D4A), L represents11Wherein the 2-valent linking group represented by L in the formulae (D1) to (D15) hasc1-alkylene-Xc1-*c2、*c1-Xc1-alkylene-)c2Orc1-Xc1-arylene-O-)c2The 2-valent linking group of the partial structure represented belongs to L11. That is, the same 2-valent linking group as L of the formula (D4) can be mentioned.
[ chemical formula 20]
In the formula (D16), A2X、A3XAnd A4XEach independently represents-CH or-N.
R17X、R18XAnd R19XIndependently represent X-X211X-(Z21X-X212X)n21X-L21X-Q. Denotes the bonding site to the central ring.
X211XAnd X212XEach 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-.
Z21XAn aromatic ring group or a 5-membered ring or a 6-membered ring each independently represents a 5-membered ring or a 6-membered ringA 6-membered non-aromatic ring group.
L21XRepresents a single bond or a 2-valent linking group.
Q each independently represents a hydrogen atom or a substituent.
Wherein 1 or more Q's represent the above reactive functional group.
n21X represents an integer of 0 to 3. When n21X is 2 or more, (Z) is present in 2 or more21X-X212X) May be the same or different.
The compound represented by the formula (D16) is as described above.
In addition, the phase transition temperature from the crystal phase to the liquid crystal phase of the liquid crystalline discotic compound is preferably 200 ℃ or lower, and more preferably 180 ℃ or lower, from the viewpoint of the curing reaction. The lower limit of the phase transition temperature from the crystal phase to the liquid crystal phase is not particularly limited, and is, for example, 0 ℃ or higher. The phase transition temperature can be confirmed by observation using a polarized light microscope or differential scanning calorimetry.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：树脂固化剂体系中的改善