Composition, thermal conductive material

Abstract

The present invention provides a composition for forming a thermally conductive material capable of providing a thermally conductive material having excellent thermal conductivity. In addition, a thermally conductive material is provided. The composition comprises a phenol compound represented by the general formula (1), an epoxy compound, and an inorganic substance. [Chemical Formula 1]

Description

Technical Field

[0001] The invention relates to a composition and a heat conducting material. Background Art

[0002] In recent years, the miniaturization of power semiconductor devices used in various electrical devices such as personal computers, general household appliances, and automobiles has been progressing rapidly. The heat generated by the power semiconductor devices that are becoming denser as they become smaller has become difficult to control.

[0003] In order to cope with such a problem, a thermally conductive material is used to promote heat dissipation from a power semiconductor device.

[0004] For example, Patent Document 1 discloses a multilayer resin sheet having a resin layer including an epoxy resin, a curing agent, and an inorganic filler (Technical Solution 1). As the curing agent, for example, a novolac resin including a compound in which catechol is linked via a methylene chain is proposed (Technical Solution 5).

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-216038 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] The present inventors have studied the multilayer resin sheet having a resin layer and the like described in Patent Document 1 and have found that there is room for improvement in thermal conductivity.

[0010] Therefore, an object of the present invention is to provide a composition capable of providing a thermally conductive material having excellent thermal conductivity.

[0011] Furthermore, another object of the present invention is to provide a thermally conductive material formed from the above composition.

[0012] Means for solving technical problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that the above-mentioned problems can be solved by the following configuration.

[0014] [1]

[0015] A composition comprising a phenol compound represented by the following general formula (1), an epoxy compound, and an inorganic substance.

[0016] [2]

[0017] The composition according to [1], wherein

[0018] In the general formula (1) described below, p represents an integer of 3 or more.

[0019] 〔3〕

[0020] The composition according to [1] or [2], wherein

[0021] The number average molecular weight of the phenol compound represented by the general formula (1) described below is 420 or less.

[0022] [4]

[0023] The composition according to any one of [1] to [3], wherein

[0024] In the general formula (1) described below, there are two or more R 1 ~R 3 When at least one of the groups is a group represented by the general formula (2) described below, the sum of the average value of p when two or more groups are present and the average value of q when two or more groups are present or not present is 4 or more.

[0025] 〔5〕

[0026] The composition according to any one of [1] to [4], wherein

[0027] The epoxy compound has an epoxy group content of 4.0 mmol / g or more.

[0028] [6]

[0029] The composition according to any one of [1] to [5], wherein

[0030] The above-mentioned inorganic substances include inorganic nitrides.

[0031] 〔7〕

[0032] The composition according to [6], wherein

[0033] The above-mentioned inorganic nitride includes boron nitride.

[0034] [8]

[0035] The composition according to [6] or [7], wherein

[0036] The content of the inorganic nitride is 50% by mass or more based on the total mass of the inorganic substance.

[0037] 〔9〕

[0038] The composition according to any one of [6] to [8], further comprising a surface modifier for the inorganic nitride.

[0039] 〔10〕

[0040] The composition according to any one of [1] to [9], further comprising a curing accelerator.

[0041]

[11]

[0042] A thermally conductive material obtained by curing the composition described in any one of [1] to

[10] .

[0043] Effects of the Invention

[0044] According to the present invention, a composition for forming a thermally conductive material capable of providing a thermally conductive material having excellent thermal conductivity can be provided.

[0045] Furthermore, according to the present invention, a thermally conductive material formed from the above composition can be provided. DETAILED DESCRIPTION

[0046] Hereinafter, the composition, the thermally conductive material-forming composition, and the thermally conductive material of the present invention will be described in detail.

[0047] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to these embodiments.

[0048] In addition, in this specification, the numerical range expressed with "to" means the range which includes the numerical value described before and after "to" as a lower limit value and an upper limit value.

[0049] In the present specification, the solid content of the composition means all components other than the solvent when the composition contains a solvent, and any component other than the solvent is regarded as a solid component even if it is a liquid component.

[0050] In addition, in the present specification, the epoxy group is a functional group also called an oxirane group, and for example, a group in which two adjacent carbon atoms of a saturated hydrocarbon ring group are bonded via an oxo group (-O-) to form an oxirane ring is also included in the epoxy group. The epoxy group may have a substituent (such as a methyl group) or may not have a substituent.

[0051] In the present specification, the term "(meth)acryloyl" means "either one or both of acryloyl and methacryloyl". In addition, the term "(meth)acrylamide" means "either one or both of acrylamide and methacrylamide".

[0052] In this specification, unless otherwise specified, an anhydride group may be a monovalent group or a divalent group. In addition, when an anhydride group represents a monovalent group, a substituent obtained by removing any hydrogen atom from an anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride may be cited. Furthermore, when an anhydride group represents a divalent group, a group represented by *-CO-O-CO-* is represented (* represents a bonding position).

[0053] In addition, in the present specification, for a substituent group that is not explicitly described as substituted or unsubstituted, the group may further have a substituent group (for example, the substituent group group Y described below) as long as the intended effect is not impaired. For example, the term "alkyl" means a substituted or unsubstituted alkyl group (an alkyl group with or without a substituent group) as long as the intended effect is not impaired.

[0054] In addition, in the present specification, when "may have a substituent", the type of the substituent, the position of the substituent and the number of the substituent are not particularly limited. As the number of substituents, for example, 1 or 2 or more can be cited. As the substituent, for example, a monovalent non-metallic atomic group other than a hydrogen atom is preferably cited, and a group selected from the following substituent group Y can be cited.

[0055] In the present specification, examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

[0056] Substituent group Y:

[0057] halogen atoms (-F, -Br, -Cl, -I, etc.), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate bases, carboxylic acid anhydride groups, cyanate groups, unsaturated polymerizable groups, epoxy groups, oxetane groups, aziridine groups, thiol groups, isocyanate groups, thioisocyanate groups, aldehyde groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyldisulfide groups, aryldisulfide groups, N-alkylamino groups, N,N-dialkylamino groups, N-arylamino groups, N,N-diarylamino groups, N-alkyl-N-arylamino groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N,N-dialkylcarbamoyl groups oxy, N,N-diarylcarbamoyloxy, N-alkyl-N-arylcarbamoyloxy, alkylthiooxy, arylthiooxy, acylthio, acylamino, N-alkylacylamino, N-arylacylamino, urea, N'-alkylurea, N',N'-dialkylurea, N'-arylurea, N',N'-diarylurea, N'-alkyl-N'-arylurea, N-alkylurea, N-arylurea, N'-alkyl-N-alkylurea, N'-alkyl-N-arylurea, N',N'-dialkyl-N-alkylurea, N',N'-dialkyl-N-arylurea, N'-aryl- N-alkylurea, N'-aryl-N-arylurea, N',N'-diaryl-N-alkylurea, N',N'-diaryl-N-arylurea, N'-alkyl-N'-aryl-N-alkylurea, N'-alkyl-N'-aryl-N-arylurea, 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,N -dialkylcarbamoyl, N-arylcarbamoyl, N,N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonic acid (-SO3H) and its conjugate base, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N,N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, sulfamoyl, N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N,N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-acylsulfamoyl and its conjugate base, N-alkylsulfonylsulfamoyl (-SO2NHSO2(alkyl)) and its conjugate base, N-arylsulfonylsulfamoyl (-SO2NHSO2(aryl)) and its conjugate base, N-alkylsulfonylcarbamoyl (-CONHSO2(alkyl)) and its conjugate base, N-arylsulfonylcarbamoyl (-CONHSO2(aryl)) and its conjugate base, alkoxysilyl (-Si(alkoxy)3), aryloxysilyl (-Si(aryloxy)3), hydroxysilyl (-Si(OH)3) and its conjugate base, phosphonyl (-PO3H2) and its conjugate base, dialkylphosphonyl (-PO3(alkyl)2), diarylphosphinoyl (-PO3(aryl)2), alkylarylphosphinoyl (-PO3(alkyl)(aryl)), monoalkylphosphinoyl (-PO3H(alkyl)) and its conjugate base, monoarylphosphinoyl (-PO3H(aryl)) and its conjugate base, phosphinoyloxy (-OPO3H2) and its conjugate base, dialkylphosphinoyloxy (-OPO3(alkyl)2), diarylphosphinoyloxy (-OPO3(aryl)2), alkylarylphosphinoyloxy (-OPO3(alkyl)(aryl)), monoalkylphosphinoyloxy (-OPO3H(alkyl)) and its conjugate base, monoarylphosphinoyloxy (-OPO3H(aryl)) and its conjugate base, cyano, nitro, aryl, alkenyl, alkynyl and alkyl. In addition, each of the above groups may further have a substituent (for example, one or more of the above groups) if possible. For example, an aryl group which may or may not have a substituent is also included as a group which can be selected from the substituent group Y.

[0058] When the group selected from the substituent group Y has carbon atoms, the number of carbon atoms in the group is, for example, 1 to 20.

[0059] The number of atoms other than hydrogen atoms possessed by the group selected from the substituent group Y is, for example, 1 to 30.

[0060] Furthermore, these substituents may be bonded to each other or to the substituted group to form a ring when possible, or may not form a ring. For example, an alkyl group (or an alkyl part in a group containing an alkyl group as a partial structure, such as an alkoxy group) may be a cyclic alkyl group (cycloalkyl group) or an alkyl group having one or more cyclic structures as a partial structure.

[0061] [Composition]

[0062] The composition of the present invention contains a phenol compound represented by the general formula (1) described below, an epoxy compound, and an inorganic substance.

[0063] The mechanism by which the composition of the present invention solves the problems of the present invention by the above-mentioned constitution is not clear, but the present inventors speculate as follows.

[0064] That is, it is presumed that the phenol compound represented by the general formula (1) has a predetermined number or more of phenolic hydroxyl groups, and therefore can form a high-density heat conduction path in the cured product (thermal conductive material) when the composition is cured, thereby contributing to the thermal conductivity of the obtained thermal conductive material.

[0065] Furthermore, the thermal conductive material obtained using the composition of the present invention also has excellent insulation and adhesiveness. Hereinafter, the obtained thermal conductive material having excellent thermal conductivity, insulation and / or adhesiveness is also referred to as having excellent effects of the present invention.

[0066] Hereinafter, the components contained in the composition will be described in detail.

[0067] [Phenol compound represented by general formula (1)]

[0068] The general formula (1) is shown below.

[0069] [Chemical formula 1]

[0070]

[0071] In the general formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group which may be substituted, an aralkyl group which may be substituted, or a group represented by the general formula (2),

[0072] Preferably R 1 and R 2 One or both of R are hydrogen atoms. 1 and R 2 When one of them is a hydrogen atom, the other is preferably a group represented by the general formula (2).

[0073] The number of carbon atoms of the alkyl group which may have the above-mentioned substituent is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6. The above-mentioned alkyl group may be any of a linear, branched, and cyclic structure. The above-mentioned alkyl group may have a cyclic structure as a partial structure. As a substituent which the above-mentioned alkyl group may have, for example, a group selected from the substituent group Y can be mentioned.

[0074] As the aralkyl group which may or may not have a substituent, for example, there can be mentioned a group in which the above-mentioned alkyl group has at least one aryl group as a substituent. The above-mentioned alkyl group may have a substituent other than the above-mentioned one aryl group. The above-mentioned one aryl group may have a substituent.

[0075] The number of ring members of one aryl group is preferably 6 to 15, and the aryl group may be a monocyclic or polycyclic ring.

[0076] The groups represented by the above general formula (2) are the groups shown below.

[0077] [Chemical formula 2]

[0078]

[0079] In the general formula (2), * represents a bonding position.

[0080] In the general formula (2), R 4 It represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.

[0081] The number of ring members of the aryl group in the aryl group which may have a substituent is preferably 6 to 15, and the aryl group may be a monocyclic or polycyclic ring. Examples of the substituent that the aryl group may have include groups selected from the substituent group Y.

[0082] As R in the general formula (2) 4 The alkyl group which may be substituted or not and the aralkyl group which may be substituted or not are, for example, respectively with R 1 and R 2 The alkyl group which may be substituted or not and the aralkyl group which may be substituted or not are the same.

[0083] In the general formula (2), k represents an integer of 0 or more.

[0084] k is preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and even more preferably 0.

[0085] In the general formula (2), q represents an integer of 0 or more.

[0086] q is preferably an integer of 1-5, more preferably an integer of 1-3.

[0087] However, the total of k and p (k+q) in the group represented by one general formula (2) is an integer of 0-5.

[0088] As the general formula (2), for example, the groups shown below are preferred.

[0089] [Chemical formula 3]

[0090]

[0091] In the general formula (1), R 3 represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a group represented by the general formula (2).

[0092] As R of the general formula (1)3 The group which can be an alkyl group which may be substituted or not, an aralkyl group which may be substituted or not, or a group represented by the general formula (2) is, for example, respectively 1 and R 2 The alkyl group which may be substituted or not, the aralkyl group which may be substituted or not, or the group represented by the general formula (2) are the same.

[0093] In the general formula (1), n ​​represents an integer of 0 or more.

[0094] n is preferably 0-5, more preferably 0-2.

[0095] When a mixture of phenol compounds represented by the general formula (1) differing only in the value of n is used, the average value of the value of n in the mixture is preferably greater than 0.0 and 5.0 or less, and more preferably greater than 0.0 and 2.0 or less.

[0096] In the general formula (1), j represents an integer of 0 or more.

[0097] j is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

[0098] In the general formula (1), p represents an integer of 2 or more.

[0099] From the viewpoint of further improving the effects of the present invention, p is preferably an integer of 2 or more, and more preferably an integer of 3 or more. The upper limit is, for example, an integer of 4 or less.

[0100] Among them, -(R 3 ) j and -(OH) p Here, j+p is an integer from 2 to 4.

[0101] In the general formula (1), there are two or more R 1 ~R 3 When all represent groups other than the group represented by the general formula (2) in which q is an integer of 1 or more (i.e., when two or more R 1 ~R 3 In the general formula (1), p is an integer of 3 or more.

[0102] In other words, in the general formula (1), all j's that exist in a plurality are 0, and there are 2 or more or no 2 or more R 1 and R 2When each independently represents a hydrogen atom, an alkyl group which may be substituted, an aralkyl group which may be substituted, or a group represented by the general formula (2) wherein q is 0, p is an integer of 3 or greater.

[0103] Furthermore, in the general formula (1), at least one of the multiple j present is an integer greater than 1, and two or more R are present or absent. 1 and R 2 Each independently represents a hydrogen atom, an alkyl group which may be substituted, an aralkyl group which may be substituted, or a group represented by the general formula (2) wherein q is 0, and a plurality of R may exist. 3 When it represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a group represented by the general formula (2) wherein q is 0, p is an integer of 3 or more.

[0104] From the viewpoint of further improving the effect of the present invention, the presence or absence of two or more R 1 ~R 3 When at least one of the groups is a group represented by the general formula (2), the sum of the average value of p when there are 2 or more of them and the average value of q when there are 2 or more of them or when there are not 2 or more of them (preferably the sum of the minimum value of p when there are 2 or more of them and the minimum value of q when there are 2 or more of them or when there are not 2 or more of them) is preferably 3 or more, more preferably 4 or more. The upper limit is, for example, 8 or less.

[0105] In the general formula (1), when n is 1 or more, there are multiple R 1 They may be the same or different. When n is 1 or more, there are multiple R 2 They may be the same or different. There are two or more p's that may be the same or different. There are multiple j's that may be the same or different. There are multiple -(R 3 ) j They can be the same or different.

[0106] In the general formula (1), when there are multiple groups represented by the general formula (2), the multiple qs may be the same or different. The multiple ks may be the same or different. The multiple -(R 4 ) k They can be the same or different.

[0107] Furthermore, in the general formula (1), one -(R 3 ) j There are multiple R 3 When (i.e., when j is an integer greater than 2), 1 -(R 3 ) j Multiple R in 3They may be the same as or different from each other.

[0108] In the general formula (2), one -(R 4 ) k There are multiple R 4 When (i.e., when k is greater than 2), 1-(R 4 ) k Multiple R in 4 They may be the same as or different from each other.

[0109] From the viewpoint of achieving more excellent effects of the present invention, the number average molecular weight of the phenol compound represented by the general formula (1) is preferably 550 or less, and more preferably 420 or less. The lower limit is, for example, 264 or more.

[0110] When the number average molecular weight is within the above range, the viscosity of the phenol compound represented by the general formula (1) is low, and the effect of removing foam from the composition becomes good. Therefore, it is believed that when the composition is cured, microbubbles that have an adverse effect on thermal conductivity are less likely to be generated in the cured product (thermal conductive material), and the thermal conductivity of the obtained thermal conductive material becomes good.

[0111] The number average molecular weight is a number average molecular weight based on a polystyrene conversion value measured by GPC (Gel Permeation Chromatography).

[0112] The lower limit of the hydroxyl content (preferably phenolic hydroxyl content) of the phenol compound represented by general formula (1) is preferably 10.0 mmol / g or more, more preferably 16.0 mmol / g or more, and the upper limit is preferably 30.0 mmol / g or less, more preferably 25.0 mmol / g or less.

[0113] The above-mentioned hydroxyl group content indicates the number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in 1 g of the compound.

[0114] Furthermore, the phenol compound represented by the general formula (1) may have an active hydrogen-containing group capable of polymerization reaction with an epoxy compound in addition to a hydroxyl group (phenolic hydroxyl group). The lower limit of the active hydrogen content (the total content of active hydrogen atoms in the active hydrogen-containing group) of the phenol compound represented by the general formula (1) is preferably 10.0 mmol / g or more, more preferably 16.0 mmol / g or more. The upper limit is preferably 30.0 mmol / g or less, more preferably 25.0 mmol / g or less.

[0115] The above-mentioned active hydrogen content indicates the number of active hydrogen atoms contained in 1 g of the compound.

[0116] The phenol compound represented by the general formula (1) may be used alone or in combination of two or more.

[0117] When the composition of the present invention contains a phenol compound represented by the general formula (1), the content of the phenol compound represented by the general formula (1) is preferably 1.0 to 35.0% by mass, more preferably 2.0 to 25.0% by mass, and even more preferably 3.0 to 12.0% by mass based on the total solid content of the composition.

[0118] Furthermore, the composition of the present invention may contain, as a compound other than the phenol compound represented by the general formula (1), a compound having a group capable of reacting with an epoxy group (also referred to as "other active hydrogen-containing compound").

[0119] When the composition of the present invention contains a phenol compound represented by the general formula (1) and other active hydrogen-containing compounds, the mass ratio of the content of the other active hydrogen-containing compounds to the content of the phenol compound represented by the general formula (1) in the composition of the present invention (content of other active hydrogen-containing compounds / content of the phenol compound represented by the general formula (1)) is preferably 0 to 1, more preferably 0 to 0.1, and even more preferably 0 to 0.08.

[0120] Examples of the other active hydrogen-containing compound include phenol compounds other than the phenol compound represented by the general formula (1) (other phenol compounds).

[0121] As other phenol compounds, for example, benzene polyols such as benzenetriol, biphenyl aralkyl type phenol resins, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenol resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins, polyphenol novolac resins synthesized from polyvalent hydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylethane resins, naphthol novolac resins, naphthol co-condensed novolac resins, naphthol cresol co-condensed novolac resins, biphenyl modified phenolic resins, biphenyl modified naphthol resins, aminotriazine modified phenolic resins or alkoxy-containing aromatic ring modified novolac resins, etc. are also preferred.

[0122] Furthermore, the other phenol compound is preferably a compound represented by any one of the general formulae (B01) to (B03) in the surface modifier described below, and is different from the compound having one or more phenolic hydroxyl groups.

[0123] The details of general formulae (B01) to (B03) will be described later.

[0124] 〔Epoxides〕

[0125] The composition of the present invention comprises an epoxy compound.

[0126] The epoxy compound is a compound having at least one epoxy group (oxiranyl group) in one molecule. The epoxy group may or may not have a substituent, if possible.

[0127] The number of epoxy groups contained in the epoxy compound in one molecule is preferably 2 or more, more preferably 2 to 40, further preferably 2 to 10, and particularly preferably 2.

[0128] The molecular weight of the epoxy compound is preferably 150 to 10,000, more preferably 150 to 2,000, and even more preferably 250 to 400.

[0129] The lower limit of the epoxy group content of the epoxy compound is preferably 2.0 mmol / g or more, more preferably 4.0 mmol / g or more, and further preferably 5.0 mmol / g or more, and the upper limit is preferably 20.0 mmol / g or less, more preferably 15.0 mmol / g or less, and further preferably 10.0 mmol / g or less.

[0130] In addition, the said epoxy group content shows the number of epoxy groups which 1g of an epoxy compound has.

[0131] The epoxy compound may or may not exhibit liquid crystallinity.

[0132] That is, the epoxy compound may be a liquid crystal compound. In other words, a liquid crystal compound having an epoxy group may also be used as the epoxy compound.

[0133] Examples of the epoxy compound (which may be a liquid crystalline epoxy compound) include a compound including at least a portion of a rod-like structure (rod-like compound) and a compound including at least a portion of a disc-like structure (disc-like compound).

[0134] Among them, rod-shaped compounds are preferred because the thermal conductivity of the obtained thermally conductive material is more excellent.

[0135] Hereinafter, the rod-shaped compound and the disc-shaped compound will be described in detail.

[0136] (Rod-like compound)

[0137] As the rod-shaped compound, i.e., epoxy compound, for example, there can be mentioned azomethine, azoxy, cyanobiphenyl, cyanophenyl ester, benzoate, cyclohexanecarboxylic acid phenyl ester, cyanophenylcyclohexane, cyano-substituted phenylpyrimidine, alkoxy-substituted phenylpyrimidine, phenyldioxane, tolan and alkenylcyclohexylbenzenonitrile. Not only the low molecular weight compounds as described above but also high molecular weight compounds can be used. The high molecular weight compound is a high molecular weight compound obtained by polymerizing a rod-shaped compound having a low molecular weight reactive group.

[0138] Preferred examples of the rod-like compound include rod-like compounds represented by the following general formula (E1).

[0139] Among them, the rod-shaped compound is preferably a compound represented by the general formula (E1).

[0140] [Chemical formula 4]

[0141]

[0142] In the general formula (E1), L E1 Each independently represents a single bond or a divalent linking group.

[0143] Among them, L E1 A divalent linking group is preferred.

[0144] The divalent linking group is preferably -O-, -S-, -CO-, -NH-, -CH=CH-, -C≡C-, -CH=N-, -N=CH-, -N=N-, an alkylene group with or without a substituent, or a group comprising a combination of two or more of these, and is more preferably -O-alkylene- or -alkylene-O-.

[0145] The alkylene group may be linear, branched, or cyclic, and is preferably a linear alkylene group having 1 to 2 carbon atoms.

[0146] There are multiple L E1 They can be the same or different.

[0147] In the general formula (E1), L E2 Each independently represents a single bond, -CH=CH-, -CO-O-, -O-CO-, -C(-CH3)=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=CH-CO-, -CO-CH=CH-, -CH=C(-CN)- or -C(-CN)=CH-.

[0148] Among them, L E2 Each independently is preferably a single bond, -CO-O- or -O-CO-.

[0149] L E2 When there are multiple LE2 They can be the same or different.

[0150] In the general formula (E1), L E3 Each independently represents a single bond, an optionally substituted 5-membered or 6-membered aromatic ring group, a 5-membered or 6-membered non-aromatic ring group, or a polycyclic group including these rings.

[0151] As L E3 Examples of aromatic ring groups and non-aromatic ring groups represented by , for example, 1,4-cyclohexanediyl, 1,4-cyclohexadienyl, 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 with or without substituents can be mentioned. In the case of 1,4-cyclohexanediyl, any isomer of the structural isomers of the trans-isomer and the cis-isomer may be used, or a mixture of any ratio may be used. Among them, the trans-isomer is preferred.

[0152] Among them, L E3 Preferred is a single bond, 1,4-phenylene or 1,4-cyclohexadienyl.

[0153] By L E3 The substituents possessed by the groups represented by 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).

[0154] When there are plural substituents, the substituents may be the same or different.

[0155] L E3 When there are multiple L E3 They can be the same or different.

[0156] In the general formula (E1), pe represents an integer of 0 or more.

[0157] When pe is an integer greater than 2, there are multiple (-L E3 -L E2 -) can be the same or different.

[0158] Among them, pe is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0159] In the general formula (E1), L E4 Each independently represents a substituent.

[0160] 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).

[0161] There are multiple L E4 They may be the same or different. Also, when le in the following description is an integer greater than 2, in the same (L E4 ) le There are multiple L E4 They may be the same or different.

[0162] In the general formula (E1), le each independently represents an integer of 0-4.

[0163] Here, le is preferably 0 to 2, respectively and independently.

[0164] A plurality of le's may be the same or different.

[0165] The rod-shaped compound preferably has a biphenyl skeleton.

[0166] (Disc-shaped compound)

[0167] The epoxy compound which is a disc-shaped compound has a disc-shaped structure at least partially.

[0168] The disc-shaped structure has at least an alicyclic ring or an aromatic ring. In particular, when the disc-shaped structure has an aromatic ring, the disc-shaped compound can form a columnar structure by forming a stacking structure based on π-π interaction between molecules.

[0169] Examples of the disc-shaped structure include terphenylene structures described in Angew. Chem. Int. Ed. 2012, 51, 7990-7993 or JP-A-7-306317, and trisubstituted benzene structures described in JP-A-2007-2220 and JP-A-2010-244038.

[0170] The disc-shaped compound preferably has three or more epoxy groups. A cured product of an epoxy compound including a disc-shaped compound having three or more epoxy groups tends to have a high glass transition temperature and high heat resistance.

[0171] The number of epoxy groups contained in the disc-shaped compound is preferably 8 or less, more preferably 6 or less.

[0172] Examples of disc-shaped compounds include compounds described in C. Destrade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981); Quarterly Chemistry General Theory, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10, Section 2 (1994) edited by the Chemical Society of Japan; B. Kohne et al., Angew. Chem. Soc. Chem. Comm., page 1794 (1985); J. Zhang et al., J. Am. Chem. Soc., vol. 116, page 2655 (1994) and Japanese Patent No. 4592225, in which at least one (preferably three or more) terminal group is an epoxy group.

[0173] Examples of the disc-shaped compound include terphenylene structures described in Angew. Chem. Int. Ed. 2012, 51, 7990-7993 and Japanese Patent Application Publication No. 7-306317, and compounds in which at least one (preferably three or more) of the terminals in a tri-substituted benzene structure is an epoxy group as described in Japanese Patent Application Publication No. 2007-2220 and Japanese Patent Application Publication No. 2010-244038.

[0174] As epoxy compounds other than the above-mentioned epoxy compounds, for example, epoxy compounds represented by the general formula (DN) can be mentioned.

[0175] [Chemical formula 5]

[0176]

[0177] In the general formula (DN), n DN It represents an integer greater than or equal to 0, preferably 0 to 5, and more preferably 1.

[0178] R DN Represents a single bond or a divalent linking group. The divalent linking group is preferably -O-, -O-CO-, -CO-O-, -S-, an alkylene group (preferably having 1 to 10 carbon atoms), an arylene group (preferably having 6 to 20 carbon atoms), or a group including a combination thereof, more preferably an alkylene group, and more preferably a methylene group.

[0179] Moreover, as an epoxy compound, the epoxy compound represented by general formula (DO) is mentioned, for example.

[0180] (XZ 1 -) m -A-(-Z 2 -Y) n (DO)

[0181] In the general formula (DO), m represents an integer of 3 or greater (preferably an integer of 3 to 20, more preferably an integer of 3 to 6).

[0182] In the general formula (DO), n represents an integer of 0 or greater (preferably an integer of 0 to 5, more preferably 0).

[0183] In the general formula (DO), X represents an epoxy group.

[0184] In the general formula (DO), Y represents a hydroxyl group.

[0185] In the general formula (DO), Z 1 and Z 2 Each independently represents a single bond or an alkylene group having 1 to 7 carbon atoms.

[0186] One or more -CH2- groups constituting the above-mentioned alkylene group may be substituted with -O-.

[0187] The alkylene group has preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

[0188] The number of carbon atoms in the alkylene group mentioned here refers to the number of carbon atoms before -CH2- constituting the alkylene group is replaced by -O-.

[0189] Among them, the atom adjacent to -O- is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

[0190] Z 1 Preferably, "-(CH 2 ) ZN -O-". "-(CH 2 ) ZN ZN in "-(CH-O-" represents an integer of 1 to 6, preferably 1 to 3, more preferably 1. 2 ) ZN -O-" is preferably "-(CH 2 ) ZN -" exists on the X side (epoxy group side).

[0191] Z 2 Preferred is a single bond.

[0192] In the general formula (DO), A represents an m+n-valent aliphatic saturated hydrocarbon group.

[0193] One or more of the -CH2- groups constituting the above-mentioned aliphatic saturated hydrocarbon group may be substituted with -O-, wherein the atom adjacent to -O- is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

[0194] One or more of the -CH< constituting the aliphatic saturated hydrocarbon group may be substituted with -N<. The atom adjacent to -N< is preferably a carbon atom, an oxygen atom or a nitrogen atom, and more preferably a carbon atom.

[0195] The aliphatic saturated hydrocarbon group has preferably 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 2 to 15 carbon atoms.

[0196] The preferred number of carbon atoms of the aliphatic saturated hydrocarbon group mentioned herein refers to the number of carbon atoms before -CH2- and / or -CH< constituting the aliphatic saturated hydrocarbon group is replaced by -O- and / or -N<.

[0197] When there are plural Xs, the plural Xs may be the same or different.

[0198] When there are plural Ys, the plural Ys may be the same or different.

[0199] Z 1 When there are multiple Z 1 They can be the same or different.

[0200] Z 2 When there are multiple Z 2 They can be the same or different.

[0201] In addition, examples of epoxy compounds include bisphenol A-type epoxy compounds as glycidyl ethers such as bisphenol A, F, S, and AD (in the above general formula (E1), "pe = 0" and "L E2 As -C(CH3)2-" compounds, etc.), bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AD ​​type epoxy compounds, etc.; hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol AD ​​type epoxy compounds, etc.; phenol novolac type glycidyl ether (phenol novolac type epoxy compound), cresol novolac type glycidyl ether (cresol novolac type epoxy compound), bisphenol A novolac type glycidyl ethers, etc.; dicyclopentadiene type glycidyl ether (dicyclopentadiene type epoxy compound); dihydroxypentadiene type glycidyl ether (dihydroxypentadiene type epoxy compound); polyhydroxyphenyl type glycidyl ether (polyhydroxyphenyl type epoxy compound); benzene polycarboxylic acid type glycidyl ester (benzene polycarboxylic acid type epoxy compound); alicyclic epoxy compounds such as 3,4:8,9-diepoxybicyclo[4.3.0]nonane; and trisphenol methane type epoxy compounds.

[0202] In addition, the epoxy compound is preferably a compound represented by any one of the general formulas (B01) to (B03) of the surface modifier for inorganic nitride described below, and is different from a compound having one or more epoxy groups (a compound represented by any one of the general formulas (B01) to (B03) having an epoxy group).

[0203] The epoxy compounds may be used alone or in combination of two or more.

[0204] When the composition of the present invention contains an epoxy compound, the content of the epoxy compound is preferably 1.0 to 25.0% by mass, more preferably 3.0 to 20.0% by mass, and even more preferably 10.0 to 20.0% by mass, based on the total solid content of the composition.

[0205] 〔Inorganic Matter〕

[0206] The composition comprises an inorganic substance.

[0207] As the inorganic substance, for example, any inorganic substance conventionally used as an inorganic filler for thermally conductive materials can be used. From the viewpoint of better thermal conductivity and insulation of the thermally conductive material, the inorganic substance preferably includes an inorganic nitride or an inorganic oxide, and more preferably includes an inorganic nitride.

[0208] The shape of the inorganic substance is not particularly limited, and may be in the form of particles, thin films, or plates. Examples of the shape of the particulate inorganic substance include rice grains, spheres, cubes, spindles, scales, aggregates, and irregular shapes.

[0209] As inorganic oxides, for example, zirconium oxide (ZrO2), titanium oxide (TiO2), silicon oxide (SiO2), aluminum oxide (Al2O3), iron oxide (Fe2O3, FeO, Fe3O4), copper oxide (CuO, Cu2O), zinc oxide (ZnO), yttrium oxide (Y2O3), niobium oxide (Nb2O5), molybdenum oxide (MoO3), indium oxide (In2O3, In2O), tin oxide (SnO2), tantalum oxide (Ta2O5), tungsten oxide (WO3, W2O5), lead oxide (PbO, PbO2), bismuth oxide (Bi2O3), cerium oxide (CeO2, Ce2O3), antimony oxide (Sb2O3, Sb2O5), germanium oxide (GeO2, GeO), lanthanum oxide (La2O3) and ruthenium oxide (RuO2) can be mentioned.

[0210] The above-mentioned inorganic oxides may be used alone or in combination of two or more.

[0211] The inorganic oxide is preferably titanium oxide, aluminum oxide or zinc oxide, more preferably aluminum oxide.

[0212] The inorganic oxide may be an oxide produced by oxidation of a metal prepared as a non-oxide under an environment or the like.

[0213] As inorganic nitrides, for example, boron nitride (BN), carbon nitride (C3N4), silicon nitride (Si3N4), gallium nitride (GaN), indium nitride (InN), aluminum nitride (AlN), chromium nitride (Cr2N), copper nitride (Cu3N), iron nitride (Fe4N), iron nitride (Fe3N), lanthanum nitride (LaN), lithium nitride (Li3N), magnesium nitride (Mg3N2), molybdenum nitride (Mo2N), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (W2N), tungsten nitride (WN2), yttrium nitride (YN) and zirconium nitride (ZrN) can be mentioned.

[0214] The inorganic nitride preferably contains an aluminum atom, a boron atom, or a silicon atom, more preferably contains aluminum nitride, boron nitride, or silicon nitride, further preferably contains aluminum nitride or boron nitride, and particularly preferably contains boron nitride.

[0215] The above-mentioned inorganic nitrides may be used alone or in combination of two or more.

[0216] The size of the inorganic material is not particularly limited, but from the viewpoint of better dispersibility of the inorganic material, the average particle size of the inorganic material is preferably 500 μm or less, more preferably 300 μm or less, and further preferably 200 μm or less. The lower limit is not particularly limited, but from the viewpoint of handleability, it is preferably 10 nm or more, and more preferably 100 nm or more.

[0217] When commercial products are used, the average particle size of the inorganic substance is the catalog value. When there is no catalog value, 100 inorganic substances are randomly selected, the particle sizes (longer diameters) of the inorganic substances are measured using an electron microscope, and the arithmetic average is calculated to obtain the above average particle size.

[0218] The inorganic substance may be used alone or in combination of two or more.

[0219] The inorganic substance preferably includes at least one of an inorganic nitride and an inorganic oxide, and more preferably includes at least an inorganic nitride.

[0220] The inorganic nitride preferably includes at least one of boron nitride and aluminum nitride, and more preferably includes at least boron nitride.

[0221] The content of the inorganic nitride (preferably boron nitride) in the inorganic substance is preferably 10% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more, relative to the total mass of the inorganic substance. The upper limit is 100% by mass or less.

[0222] The inorganic oxide is preferably aluminum oxide.

[0223] From the viewpoint of further improving the thermal conductivity of the thermally conductive material, the composition more preferably contains at least an inorganic substance having an average particle size of 20 μm or more (preferably 40 μm or more).

[0224] The content of the inorganic substance in the composition is preferably 40 to 95% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 95% by mass, based on the total solid content of the composition.

[0225] 〔Surface modifier〕

[0226] From the viewpoint of further improving the thermal conductivity of the thermally conductive material, the composition of the present invention may further contain a surface modifier.

[0227] The surface modifier is a component that modifies the surface of the above-mentioned inorganic substance (for example, inorganic nitride and / or inorganic oxide).

[0228] In this specification, "surface modification" means the state in which an organic substance is adsorbed on at least a part of the surface of an inorganic substance. The form of adsorption is not particularly limited, as long as it is a bonding state. That is, surface modification also includes the state in which an organic group obtained by the detachment of a part of the organic substance is bonded to the surface of an inorganic substance. Bonding can be any bond among covalent bonds, coordination bonds, ionic bonds, hydrogen bonds, van der Waals bonds and metallic bonds. Surface modification can form a monomolecular film on at least a part of the surface. A monomolecular film is a monolayer film formed by chemical adsorption of organic molecules, and is famous for Self-Assembled MonoLayer (SAM). In addition, in this specification, surface modification can be only a part of the surface of an inorganic substance, or it can be a whole. In this specification, "surface modified inorganic substance" means an inorganic substance surface-modified by a surface modifier, i.e., a substance in which an organic substance is adsorbed on the surface of an inorganic substance.

[0229] The surface modifier may be a surface modifier of an inorganic nitride (surface modifier for inorganic nitride) or a surface modifier of an inorganic oxide (surface modifier for inorganic oxide).

[0230] That is, in the composition of the present invention, the inorganic substance may constitute a surface-modified inorganic substance (preferably a surface-modified inorganic nitride and / or a surface-modified inorganic oxide) together with the surface modifier.

[0231] As surface modifier, for example, previously known surface modifiers such as carboxylic acids, organic phosphonic acids, organic phosphates, organosilane molecules (silane coupling agents) such as long-chain alkyl fatty acids can be used. In addition, for example, the surface modifiers described in Japanese Unexamined Patent Publication No. 2009-502529, Japanese Unexamined Patent Publication No. 2001-192500, and Patent No. 4694929 can be utilized.

[0232] Furthermore, it is preferred (preferably when the inorganic substance includes an inorganic nitride (boron nitride and / or aluminum nitride, etc.)) that the composition includes a compound having a fused ring skeleton (preferably a fused ring skeleton in which aromatic rings are fused to each other) or a compound having a triazine skeleton as a surface modifier.

[0233] That is, these compounds are preferably used as surface modifiers for inorganic nitrides.

[0234] <Surface Modifier A>

[0235] The surface modifier (preferably a surface modifier for inorganic nitrides) is preferably a surface modifier A described below. In addition, the surface modifier A is a surface modifier having a condensed ring skeleton.

[0236] The surface modifier A satisfies the following conditions 1 and 2.

[0237] Condition 1: Having a functional group selected from the functional group group P shown below (hereinafter also referred to as "specific functional group A").

[0238] (Functional Group P)

[0239] The alkylene oxide is selected from the group consisting of boric acid group (-B(OH)2), aldehyde group (-CHO), isocyanate group (-N=C=O), isothiocyanate group (-N=C=S), cyanate group (-O-CN), acyl azide group (Acyl azide), succinimidyl group, sulfonyl chloride group (-SO2Cl), carboxylic acid chloride group (-COCl), onium group, carbonate group (-O-CO-O-), halogenated aromatic group, carbodiimide group (-N=C=N-), anhydride group (-CO-O-CO- or monovalent anhydride groups such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride), carboxylic acid group (-COOH), phosphonic acid group (-PO(OH)2), phosphinic acid group (-HPO(OH)), phosphoric acid group (-OP(=O)(OH)2), phosphate ester group (-OP(=O)(OR B )2), sulfonic acid group (-SO3H), alkyl halide, nitrile group (-CN), nitro group (-NO2), ester group (-CO-O- or -O-CO-), carbonyl group (-CO-), imidoester group (-C(=NR C )-O- or -OC(=NR C)-), alkoxysilyl, acrylic group (-OCOCH2=CH2), methacryloyl group (-OCOCH(CH3)=CH2), oxetanyl, vinyl (-CH=CH2), alkynyl (a group in which one hydrogen atom is removed from alkyne. For example, it includes ethynyl and prop-2-yn-1-yl, etc.), maleimide group, thiol group (-SH), hydroxyl group (-OH), halogen atoms (F atoms, Cl atoms, Br atoms and I atoms) and amino groups.

[0240] The above-mentioned acylazido group represents a group represented by the following structure. In addition, * in the formula represents a bonding position. - ), for example, halogen ions can be mentioned.

[0241] [Chemical formula 6]

[0242]

[0243] The succinimidyl group, oxetanyl group and maleimide group respectively represent groups formed by removing a hydrogen atom at an arbitrary position from a compound represented by the following formula.

[0244] [Chemical formula 7]

[0245]

[0246] Furthermore, the onium group refers to a group having an onium salt structure. An onium salt is a compound formed by a compound having an electron pair that does not participate in a chemical bond and another cationic compound through a coordination bond between the electron pair. Generally, an onium salt contains a cation and an anion.

[0247] As the onium salt structure, for example, ammonium salt structure, pyridinium salt structure, imidazolium salt structure, pyrrolidinium salt structure, piperidinium salt structure, triethylenediamine salt structure, phosphonium salt structure, sulfonium salt structure and thiopyrylium salt structure can be cited. In addition, the type of the anion that becomes the counter is not particularly limited, and a known anion can be used. As the valence of the anion, for example, 1 to 3 valences can be cited, preferably 1 to 2 valences.

[0248] Among them, the onium group is preferably a group having an ammonium salt structure represented by the following general formula (A1).

[0249] [Chemical formula 8]

[0250]

[0251] In the general formula (A1), R 1A ~R 3AEach independently represents a hydrogen atom or an alkyl group (including any of linear, branched, and cyclic groups). The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3. - represents an anion. * represents a bonding position. In addition, the alkyl group may further have a substituent (for example, substituent group Y).

[0252] The above-mentioned halogenated aryl group is not particularly limited as long as it is a group in which one or more halogen atoms are substituted on the aromatic ring group. The above-mentioned aromatic ring group can be any one of a monocyclic structure and a polycyclic structure, preferably a phenyl group. In addition, the halogen atom can include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom. In addition, the halogenated aryl group can further have a substituent (for example, a substituent group Y).

[0253] Examples of the halogenated aryl group include a fluorophenyl group, a perfluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group.

[0254] The above phosphate group is only required to be -OP(=O)(OR B )2 is not particularly limited. B , may be a hydrogen atom or a monovalent organic group. B Any one or more of represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group (including any of a linear, branched, and cyclic group) and an aryl group. The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3. In addition, the alkyl group may further have a substituent (for example, a substituent group Y). Examples of the aryl group include a phenyl group and a pyrenyl group.

[0255] Examples of the halogenated alkyl group include groups in which one or more halogen atoms are substituted by an alkyl group having 1 to 10 carbon atoms. The alkyl group (including any of a linear, branched, and cyclic group) preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of the halogenated alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom. In addition, the halogenated alkyl group may further have a substituent (e.g., substituent group Y).

[0256] The above-mentioned imidoester group is only required to be -C(=NR C )-O- or -OC(=NR C )-, there is no particular limitation. C , for example, a hydrogen atom and an alkyl group (including any of linear, branched and cyclic ones). The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3. In addition, the alkyl group may further have a substituent (for example, substituent group Y).

[0257] In addition, in the imidoester group, an electron pair that does not participate in chemical bonding with imine nitrogen may be coordinately bonded with another cation (eg, hydrogen ion) to form an onium salt structure.

[0258] Examples of the alkoxysilyl group include groups represented by the following general formula (A2).

[0259] General formula (A2): *-Si(OR D )3

[0260] In the general formula (A2), R D Each independently represents an alkyl group (including linear, branched, and cyclic ones). * represents a bonding position.

[0261] As R D Examples of the alkyl group represented by include alkyl groups having 1 to 10 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms.

[0262] Specific examples include a trimethoxysilyl group and a triethoxysilyl group.

[0263] In addition, the alkyl group may further have a substituent (for example, substituent group Y).

[0264] The amino group may be any of primary, secondary and tertiary amino groups. E )2(R E Each independently represents a hydrogen atom or an alkyl group (including any of linear, branched, and cyclic ones). The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3. The alkyl group may further have an amino group represented by a substituent (for example, substituent group Y).

[0265] In the surface modifier A, the number of the specific functional groups A is not particularly limited as long as it is 1 or more. Also, the upper limit is not particularly limited, but is preferably 15 or less. Among them, from the viewpoint of better dispersibility of the surface-modified inorganic substance (preferably the surface-modified inorganic nitride), it is preferably 1 to 8, more preferably 1 to 3, and even more preferably 1 or 2.

[0266] · Condition 2: having a condensed ring structure including two or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0267] Examples of the aromatic hydrocarbon ring include monocyclic aromatic hydrocarbon rings having 5 or more members. The upper limit of the number of ring members is not particularly limited, and is often 10 or less. The aromatic hydrocarbon ring is preferably a monocyclic aromatic hydrocarbon ring having 5 or 6 members.

[0268] Examples of the aromatic hydrocarbon ring include a cyclopentadiene ring and a benzene ring.

[0269] As the aromatic heterocycle, for example, a monocyclic aromatic heterocycle having 5 or more members can be cited. The upper limit of the number of ring members is not particularly limited, and the number of ring members is often 10 or less. As the aromatic heterocycle, for example, a monocyclic aromatic heterocycle having 5 or 6 members is preferred.

[0270] Examples of the aromatic heterocyclic ring include a thiophene ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring.

[0271] The above-mentioned condensed ring structure is not particularly limited as long as it is a condensed ring structure containing more than 2 rings selected from the group including aromatic hydrocarbon rings and aromatic heterocycles. Among them, from the viewpoint of more excellent effect of the present invention, it is preferably a condensed ring structure containing more than 2 rings of aromatic hydrocarbon rings, more preferably a condensed ring structure containing more than 2 rings of benzene rings, and further preferably a condensed ring structure containing more than 3 rings of benzene rings. In addition, as the upper limit of the number of aromatic hydrocarbon rings and aromatic heterocycles contained in the above-mentioned condensed structure, for example, there are many cases where the number is less than 10.

[0272] The condensed ring structure containing two or more aromatic hydrocarbon rings is preferably a condensed ring structure including a condensed ring selected from the group consisting of biphenylene, indenes, acenaphthylene, fluorene, phenanthrene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, pyrene, chrysene, condensed tetraphenylene, pleiadene, phenanthene, perylene, pentaphenylene, condensed pentacene, tetraphenylene, hexylphenene and triphenylene. From the viewpoint of more excellent effects of the present invention, among the above, a condensed ring structure including a condensed ring containing two or more benzene rings is more preferred, a condensed ring structure including a condensed ring containing three or more benzene rings is further preferred, and a condensed ring structure including pyrene or perylene is particularly preferred.

[0273] From the viewpoint of further improving dispersibility, the surface modifier A is preferably a compound represented by the general formula (V1), and more preferably a compound represented by the general formula (V2).

[0274] Hereinafter, the compound represented by the general formula (V1) and the compound represented by the general formula (V2) will be described respectively.

[0275] (Compound represented by general formula (V1))

[0276] [Chemical formula 9]

[0277]

[0278] In the general formula (V1), X represents an n-valent organic group having a condensed ring structure including two or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0279] The above X represents an n-valent organic group (n is an integer greater than 1). There is no particular limitation on n as long as it is an integer greater than 1. In addition, its upper limit is not particularly limited, but is preferably an integer less than 15. Among them, from the viewpoint of better dispersibility of the surface-modified inorganic substance (preferably the surface-modified inorganic nitride), it is preferably 1 to 8, more preferably 1 to 3, and even more preferably 1 or 2.

[0280] Examples of the condensed ring structure including two or more rings selected from the group consisting of the aromatic hydrocarbon ring and the aromatic heterocyclic ring in X include the above-mentioned structures, and preferred embodiments are also the same.

[0281] The n-valent organic group represented by X is not particularly limited as long as it has a condensed ring structure including two or more rings selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. From the viewpoint of further improving the effect of the present invention, it is preferably a group formed by extracting n hydrogen atoms from a condensed ring including two or more rings selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings.

[0282] Furthermore, the condensed ring structure may further have a substituent (for example, a substituent group Y) in addition to the specific functional group A.

[0283] The above-mentioned Y represents a monovalent group represented by the following general formula (B1), a monovalent group represented by the following general formula (B2), or a monovalent group represented by the following general formula (B4), or, when n represents an integer greater than 2, represents a divalent group represented by the following general formula (B3) in which a plurality of Ys are bonded.

[0284] In other words, when n is 1, the above Y represents a monovalent group represented by the following general formula (B1), a monovalent group represented by the following general formula (B2), or a monovalent group represented by the following general formula (B4).

[0285] When n represents an integer greater than 2, the above Y represents a monovalent group represented by the following general formula (B1), a monovalent group represented by the following general formula (B2), or a monovalent group represented by the following general formula (B4), or a divalent group represented by the following general formula (B3) formed by bonding a plurality of Y. In addition, when n is greater than 2, the plurality of Ys may be the same or different.

[0286] When Y represents a divalent group represented by the following general formula (B3), the compound represented by the general formula (V1) is represented by the following general formula (V3).

[0287] [Chemical formula 10]

[0288]

[0289] In the general formula (V3), X has the same meaning as X in the above general formula (V1). 3 and L in the general formula (B3) described below 3 have the same meaning.

[0290] General formula (B1): * 1 -L 1 -P 1

[0291] In the general formula (B1), L 1 It represents a single bond or a divalent linking group.

[0292] Examples of the divalent linking group include -O-, -S-, and -NR F -(R F represents a hydrogen atom or an alkyl group. ), a divalent hydrocarbon group (e.g., an alkylene group, an alkenylene group (e.g., -CH=CH-), an alkynylene group (e.g., -C≡C-) and an arylene group), a divalent organic group in the above functional group group P (a carbonate group (-O-CO-O-), a carbodiimide group (-N=C=N-), an anhydride group (-CO-O-CO-), an ester group (-CO-O- or -O-CO-), a carbonyl group (-CO-), an acylidene group (-C(=NR C )-O- or -OC(=NR C )-)) or a group consisting of combinations thereof.

[0293] Examples of the above-mentioned combined groups include -(divalent hydrocarbon group)-X 111 -、-X 111 -(divalent hydrocarbon group)-, -(divalent hydrocarbon group)-X 111 -(divalent hydrocarbon group)-, -X 111 -(Divalent hydrocarbon group)-X 111 -(divalent hydrocarbon group)- or -(divalent hydrocarbon group)-X 111 -(Divalent hydrocarbon group)-X 111 - etc. In addition, -X 111 - is -O-, -S-, -NR F -, a divalent organic group or a group formed by combining these in the above functional group P. The total number of carbon atoms in the above group formed by combining is, for example, 1 to 20, and preferably 1 to 12.

[0294] The above P 1The functional group P includes a monovalent organic group (boric acid group (-B(OH)2), aldehyde group (-CHO), isocyanate group (-N=C=O), isothiocyanate group (-N=C=S), cyanate group (-O-CN), acyl azide group, succinimide group, sulfonyl chloride group (-SO2Cl), carboxylic acid chloride group (-COCl), onium group, halogenated aromatic group, acid anhydride group (including monovalent acid anhydride groups such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride), carboxylic acid group (-COOH), phosphonic acid group (-PO(OH)2), phosphinic acid group (-HPO(OH)), phosphoric acid group (-OP(=O)(OH)2), phosphate ester group (-OP(=O)(OR B )2), sulfonic acid group (-SO3H), halogenated alkyl group, nitrile group (-CN), nitro group (-NO2), alkoxysilyl group, acrylic group (-OCOCH2=CH2), methacryloyl group (-OCOCH(CH3)=CH2), oxetanyl group, vinyl group (-CH=CH2), alkynyl group (a group in which one hydrogen atom is removed from alkyne. For example, it includes ethynyl and prop-2-yn-1-yl, etc.), maleimide group, thiol group (-SH), hydroxyl group (-OH), halogen atoms (F atom, Cl atom, Br atom and I atom)).

[0295] * 1 represents the bonding position to the above-mentioned X.

[0296] General formula (B2): * 2 -L 2 -P 2

[0297] In the general formula (B2), L 2 represents a divalent organic group (carbonate group (-O-CO-O-), carbodiimide group (-N=C=N-), anhydride group (-CO-O-CO-), ester group (-CO-O- or -O-CO-), carbonyl group (-CO-) or acylide ester group (-C(=NR C )-O- or -OC(=NR C )-)) is a divalent linking group.

[0298] As the above L 2 For example, the divalent organic group in the functional group group P or a combination of the divalent organic group in the functional group group P and a selected group including -O-, -S-, -NR F -(R F represents a hydrogen atom or an alkyl group. ) and a divalent hydrocarbon group (for example, an alkylene group, an alkenylene group (for example: -CH=CH-), an alkynylene group (for example: -C≡C-) and an arylene group) formed by connecting a group.

[0299] Examples of the above-mentioned combined groups include -(divalent hydrocarbon group)-X 112 - etc. In addition, -X 112 - is a divalent organic group in the functional group group P or a combination of a divalent organic group in the functional group group P and a group selected from -O-, -S- and -NR F The total number of carbon atoms in the above-mentioned combined group is, for example, 1 to 20, preferably 1 to 12.

[0300] The above P 2 represents a monovalent organic group. 2 The monovalent organic group represented by is, for example, an alkyl group. The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3.

[0301] * 2 represents the bonding position to the above-mentioned X.

[0302] General formula (B3): * 31 -L 3 -* 32

[0303] In the general formula (B3), L 3 represents a divalent organic group (carbonate group (-O-CO-O-), carbodiimide group (-N=C=N-), anhydride group (-CO-O-CO-), ester group (-CO-O- or -O-CO-), carbonyl group (-CO-) or acylide ester group (-C(=NR C )-O- or -OC(=NR C )-)) is a divalent linking group.

[0304] As the above L 3 For example, the divalent organic group in the functional group group P or a combination of the divalent organic group in the functional group group P and a selected group including -O-, -S-, -NR F -(R F represents a hydrogen atom or an alkyl group. ) and a divalent hydrocarbon group (for example, an alkylene group, an alkenylene group (for example: -CH=CH-), an alkynylene group (for example: -C≡C-) and an arylene group) formed by connecting a group.

[0305] Examples of the above-mentioned combined groups include -(divalent hydrocarbon group)-X 113 -(divalent hydrocarbon group)-, -(divalent hydrocarbon group)-X 113 -、-X 113 -(divalent hydrocarbon group)- and -X 113 -(Divalent hydrocarbon group)-X113 - etc. In addition, -X 113 - is a divalent organic group in the functional group group P or a combination of a divalent organic group in the functional group group P and a group selected from -O-, -S- and -NR F The total number of carbon atoms in the above-mentioned combined group is, for example, 1 to 20, preferably 1 to 12.

[0306] * 31 and* 32 represents the bonding position with the above X. That is, the above L 3 Two carbon atoms different from the condensed ring structure represented by X above form a ring together.

[0307] General formula (B4):

[0308] [Chemical formula 11]

[0309]

[0310] In the general formula (B4), L 4 Indicates m 11 +1-valent linking group.

[0311] m 11 represents an integer greater than 2. As m 11 The upper limit value is, for example, 100 or less, preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. 11 The lower limit of is preferably 4 or more.

[0312] As L 4 The linking group represented by 11 + a monovalent aromatic hydrocarbon ring or a group represented by the following general formula (M1).

[0313] [Chemical formula 12]

[0314]

[0315] In the above general formula (M1), X 221 and X 222 Each independently represents a single bond or a divalent linking group. 221 and X 222 The divalent linking group represented by 1 The divalent linking group represented by has the same meaning as that of .

[0316] E 221 represents a substituent. 221 Examples of the substituent represented by include the groups exemplified in the substituent group Y.

[0317] m 221 represents an integer from 2 to 5. 221 Preferably 2 or 3.

[0318] m 222 Indicates an integer from 0 to 3.

[0319] Among them, m 221 +m 222 Indicates an integer from 2 to 5.

[0320] * 41 represents the bonding position to the above-mentioned X.

[0321] * 42 Indicates that the above P 4 bonding position.

[0322] Among the groups represented by the above-mentioned general formula (M1), groups represented by the following general formula (M2) are preferred.

[0323] [Chemical formula 13]

[0324]

[0325] In the above general formula (M2), X 223 , X 224 and X 225 Each independently represents a single bond or a divalent linking group. 223 , X 224 and X 225 The divalent linking group represented by 1 The divalent linking group represented by has the same meaning as that of .

[0326] E 222 and E 223 Each independently represents a substituent. 222 and E 223 Examples of the substituent represented by include the groups exemplified in the substituent group Y.

[0327] m 223 represents an integer from 1 to 5. 223 Preferably 2 or 3.

[0328] m 224 Indicates an integer from 0 to 3.

[0329] m 225 Indicates an integer from 0 to 4.

[0330] m 226 represents an integer from 2 to 5. 226 Preferably 2 or 3.

[0331] Among them, m 224 +m 226 represents an integer from 2 to 5. And, m 223 +m 225 Indicates an integer from 1 to 5.

[0332] * 41 represents the bonding position to the above-mentioned X.

[0333] * 42 Indicates that the above P 4 bonding position.

[0334] The above P 4 With the above general formula (B1) P 1 have the same meaning.

[0335] * 4 represents the bonding position to the above-mentioned X.

[0336] (Compound represented by general formula (V2))

[0337] [Chemical formula 14]

[0338]

[0339] In the general formula (V2), X 11 Indicates n with a condensed ring structure 11 +n 12 The fused ring structure is an organic group having a valence of 2 or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0340] The above X 11 Indicates n 11 +n 12 Valence organic group (n 11 、n 12 are each independently an integer greater than 1). 11 、n 12 There is no particular limitation as long as each independently represents an integer greater than 1. 11 +n 12 The upper limit of is not particularly limited, but is preferably an integer of 15 or less. Among them, 2 to 8 are preferred, 2 to 3 are more preferred, and 2 is further preferred from the viewpoint of better dispersibility of the surface-modified inorganic substance.

[0341] As included selected from the above X 11 Examples of the condensed ring structure of two or more rings in the group of the aromatic hydrocarbon ring and the aromatic heterocyclic ring include the above-mentioned structures, and preferred embodiments are also the same.

[0342] By the above X11 n 11 +n 12 The organic group having a valent structure is not particularly limited as long as it has a condensed ring structure including two or more rings selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. However, from the viewpoint of achieving a more excellent effect of the present invention, it is preferred to extract n from the condensed ring structure including two or more rings selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. 11 +n 12 A group formed by hydrogen atoms.

[0343] In addition, in addition to Y 11 and Y 12 In addition, the condensed ring structure may further have a substituent (eg, substituent group Y).

[0344] The above Y 11 It contains a functional group selected from the following functional group group Q. The functional groups listed in the following functional group group Q correspond to the functional groups listed in the above functional group group P, which tend to have excellent adsorption properties to inorganic substances (especially, inorganic nitrides).

[0345] Furthermore, the above Y 12 The functional group includes a functional group selected from the following functional group group R. The functional groups listed in the following functional group group R correspond to the functional groups listed in the above functional group group P that have a function of easily accelerating the curing of the composition.

[0346] (Functional Group Q)

[0347] selected from the group consisting of a boric acid group (-B(OH)2), an aldehyde group (-CHO), an isocyanate group (-N=C=O), an isothiocyanate group (-N=C=S), a cyanate group (-O-CN), an acyl azide group, a succinimidyl group, a sulfonyl chloride group (-SO2Cl), a carboxylic acid chloride group (-COCl), an onium group, a carbonate group (-O-CO-O-), a halogenated aromatic group, a carbodiimide group (-N=C=N-), an anhydride group (-CO-O-CO- or a monovalent anhydride group such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride), a phosphonic acid group (-PO(OH)2), a phosphinate group (-HPO(OH)), a phosphoric acid group (-OP(=O)(OH)2), a phosphate ester group (-OP(=O)(OR B )2), sulfonic acid group (-SO3H), alkyl halide, nitrile group (-CN), nitro group (-NO2), ester group (-CO-O- or -O-CO-), carbonyl group (-CO-), imidoester group (-C(=NR C )-O- or -OC(=NR C )-) and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom).

[0348] (Functional group R)

[0349] A functional group selected from the group consisting of a carboxylic acid group (-COOH), an alkoxysilyl group, an acrylic group (-OCOCH2=CH2), a methacryloyl group (-OCOCH(CH3)=CH2), an oxetane group, a vinyl group (-CH=CH2), an alkynyl group (a group in which a hydrogen atom is removed from an alkyne. For example, it includes an ethynyl group and a prop-2-yn-1-yl group, etc.), a maleimide group, a thiol group (-SH), a hydroxyl group (-OH) and an amine group.

[0350] In the general formula (V2), specifically, the above Y 11 represents a monovalent group represented by the following general formula (C1) or a monovalent group represented by the following general formula (C2), or, in n 11 When an integer greater than 2 is indicated, it indicates multiple Y 11 A divalent group represented by the following general formula (C3) formed by bonding.

[0351] In other words, in n 11 When Y is 1, 11 represents a monovalent group represented by the following general formula (C1) or a monovalent group represented by the following general formula (C2). 11 When Y represents an integer greater than 2, 11 represents a monovalent group represented by the following general formula (C1) or a monovalent group represented by the following general formula (C2), or represents a plurality of Y 11 A divalent group represented by the following general formula (C3) formed by bonding. 11 When the value is 2 or more, there are multiple Y 11 They may be the same or different.

[0352] In addition, in Y 11 When a divalent group represented by the following general formula (C3) is represented, the compound represented by the general formula (V2) is represented by the following general formula (V4).

[0353] [Chemical formula 15]

[0354]

[0355] In the general formula (V4), X 11 , Y 12 and n 12 and X in the above general formula (V2) 11 , Y 12 and n 12 and M 3 and M in the general formula (C3) described below 3 have the same meaning.

[0356] General formula (C1): * 1 -M 1 -Q 1

[0357] In the general formula (C1), M 1 represents a single bond or a divalent linking group. 1 The divalent linking group represented by 1 The meanings are the same, and the preferences are also the same.

[0358] The above Q 1 The functional group Q includes a monovalent organic group (boric acid group (-B(OH)2), aldehyde group (-CHO), isocyanate group (-N=C=O), isothiocyanate group (-N=C=S), cyanate group (-O-CN), acyl azide group, succinimidyl group, sulfonyl chloride group (-SO2Cl), carboxylic acid chloride group (-COCl), onium group, halogenated aromatic group, acid anhydride group (including monovalent acid anhydride groups such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride), phosphonic acid group (-PO(OH)2), phosphinic acid group (-HPO(OH)), phosphoric acid group (-OP(=O)(OH)2), phosphate ester group (-OP(=O)(OR B )2), sulfonic acid group (-SO3H), halogenated alkyl group, nitrile group (-CN), nitro group (-NO2) or halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom)). * 1 Indicates that the above X 11 bonding position.

[0359] General formula (C2): * 2 -M 2 -Q 2

[0360] In the general formula (C2), M 2 With the above L 2 has the same meaning and the preferred mode is also the same. 2 represents a monovalent organic group. 2 The monovalent linking group represented by 2 has the same meaning and the same preferred aspects. * 2 Indicates that the above X 11 bonding position.

[0361] General formula (C3): * 31 -M 3 -* 32

[0362] In the general formula (C3), M 3 With the above L3 has the same meaning and the same preferred aspects. * 31 and* 32 Indicates that the above X 11 That is, the above M 3 With the above X 11 The fused ring structure represented by the two carbon atoms are different and together form a ring.

[0363] The above Y 12 It represents a monovalent group represented by the following general formula (D1) or a monovalent group represented by the following general formula (D2).

[0364] General formula (D1): * 1 -W 1 -R 1

[0365] In the general formula (D1), W 1 represents a single bond or a divalent linking group. 1 represents a carboxylic acid group, an alkoxysilyl group, an acrylic group, a methacryloyl group, an oxetanyl group, a vinyl group, an alkynyl group, a maleimide group, a thiol group, a hydroxyl group or an amino group. * 1 Indicates that the above X 11 In addition, the above R 1 It represents the functional group mentioned in the functional group group R above.

[0366] As W 1 The divalent linking group represented by 1 The meanings are the same, and the preferences are also the same.

[0367] * 1 Indicates that the above X 11 bonding position.

[0368] General formula (D2):

[0369] [Chemical formula 16]

[0370]

[0371] In the general formula (D2), W 2 Indicates m 21 +1-valent linking group.

[0372] m 21 represents an integer greater than 2. As m 21 The upper limit value is, for example, 100 or less, preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. 21 The lower limit of is preferably 4 or more.

[0373] R 2represents a carboxylic acid group, an alkoxysilyl group, an acrylic group, a methacryloyl group, an oxetanyl group, a vinyl group, an alkynyl group, a maleimide group, a thiol group, a hydroxyl group or an amino group. 2 It represents the functional group mentioned in the functional group group R above.

[0374] As W 2 m 21 +1-valent linking group, for example, 4 The meanings are the same, and the preferences are also the same.

[0375] * 2 Indicates that the above X 11 bonding position.

[0376] The molecular weight of the surface modifier A is, for example, 150 or more, preferably 200 or more from the viewpoint of better dispersibility of the surface-modified inorganic substance (preferably the surface-modified inorganic nitride), and preferably 2,000 or less, more preferably 1,000 or less from the viewpoint of solubility.

[0377] <Surface modifier B>

[0378] The surface modifier (preferably a surface modifier for inorganic nitrides) is also preferably a surface modifier B described below.

[0379] The surface modifier B is a compound represented by the general formula (B01).

[0380] (Compound represented by general formula (B01))

[0381] X B -[-(L 1B ) mB -Z B ] nB (B01)

[0382] In the general formula (B01), mB represents an integer greater than or equal to 0 (preferably 0 to 10). When mB is 0, Z B With X B Direct bonding.

[0383] nB represents an integer of 3-6.

[0384] X B It represents a benzene ring group or a heterocyclic group (preferably a triazine ring group) which may have a substituent.

[0385] L 1B represents an arylene group, an ester group, an ether group, a thioester group, a thioether group, a carbonyl group, -NR N -, an azo group or an unsaturated hydrocarbon group which may have a substituent. (RN represents a hydrogen atom or a substituent)

[0386] Z B It represents an aromatic ring group which may have a substituent.

[0387] A plurality of mBs may be the same or different.

[0388] L 1B When there are multiple L 1B They can be the same or different.

[0389] There are multiple Z B They can be the same or different.

[0390] (Compound represented by general formula (B02))

[0391] Among them, the surface modifier B is preferably a compound represented by the general formula (B02).

[0392] [Chemical formula 17]

[0393]

[0394] In the general formula (B02), E 1 ~E 3 Each independently represents a single bond, -NH- or -NR-.

[0395] R represents a substituent (preferably a linear or branched alkyl group having 1 to 5 carbon atoms). 1 ~E 3 When there are a plurality of -NR-, the plurality of R's may be the same or different.

[0396] Among them, from the viewpoint of obtaining a thermally conductive material with better thermal conductivity, E 1 ~E 3 Each of them is independently preferably a single bond or -NH-. This is considered to be because E 1 ~E 3 In the case of the above groups, the interaction between the compound represented by the general formula (B02) and the inorganic substance (particularly the inorganic nitride) becomes further enhanced.

[0397] In the general formula (B02), B 1 ~B 3 Each independently represents a ring member atom which may have a substituent, that is, an aromatic ring group having 6 or more carbon atoms.

[0398] In addition, B 1 ~B 3 On the ring atoms of the above aromatic ring group, respectively 1 ~E3 and X 1 ~X 3 Bonding.

[0399] The above aromatic ring group may be a monocyclic aromatic ring group or a polycyclic aromatic ring group.

[0400] The monocyclic aromatic ring group preferably has 6 to 10 ring members.

[0401] The number of rings constituting the polycyclic aromatic ring group is preferably 2 to 4, more preferably 2. The number of ring members constituting the polycyclic aromatic ring group is preferably 5 to 10, respectively, independently.

[0402] The aromatic ring group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0403] The number of heteroatoms in the aromatic heterocyclic group is preferably 1 to 5. Examples of the heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon and boron atoms, and among them, nitrogen, sulfur or oxygen is preferred.

[0404] B 1 ~B 3 The substituent that the aromatic ring group may have is preferably a group other than the substituent represented by the general formula (B2R) described later. 1 Directly bonded B 1 The atoms in B are adjacent to each other. 1 When the atom in E has a substituent, the substituent may be a hydroxyl group. 2 Directly bonded B 2 The atoms in B are adjacent to each other. 2 When the atom in E has a substituent, the substituent may be a hydroxyl group. 3 Directly bonded B 3 The atoms in B are adjacent to each other. 3 When the atom in has a substituent, the substituent may be a hydroxyl group.

[0405] B 1 ~B 3 When the aromatic ring group has a plurality of substituents, the plurality of substituents may be bonded to each other to form a non-aromatic ring.

[0406] By B 1 ~B 3 The number of carbon atoms in the aromatic ring group represented by is 6 or more (preferably 6 to 12). The number of carbon atoms in the ring group represents the number of carbon atoms in the ring group constituting the aromatic ring.

[0407] In addition, when the aromatic ring group has multiple substituents and the multiple substituents are bonded to each other to form a non-aromatic ring, the number of carbon atoms contained only in the non-aromatic ring is not counted as the number of carbon atoms as the ring member atoms. In addition, the carbon atoms shared by the aromatic ring and the non-aromatic ring in the aromatic ring group are counted as the number of carbon atoms as the ring member atoms.

[0408] As B 1 ~B 3 For example, a benzene ring group, a naphthyl ring group, an anthracene ring group, a benzothiazole ring group, a carbazole ring group, and an indole ring group can be mentioned.

[0409] Among them, B 1 ~B 3 Each independently preferably is a benzene ring group or a naphthyl ring group.

[0410] In the general formula (B02), lb, mb and nb each independently represent an integer greater than or equal to 0.

[0411] lb, mb and nb are each independently preferably 0-5, more preferably 1-2.

[0412] In addition, when lb is 0, B 1 Does not have X 1 When mb is 0, B 2 Does not have X 2 When nb is 0, B 3 Does not have X 3 .

[0413] For example, when mb is 0, the compound represented by the general formula (B02) is a compound represented by the following general formula.

[0414] [Chemical formula 18]

[0415]

[0416] When lb is 2 or more (i.e., X 1 There are multiple (1b) X 1 They may be the same or different. When mb is 2 or more (i.e., X 2 There are multiple (mb) X 2 They may be the same or different. When nb is 2 or more (i.e., X 3 There are multiple (nb) X 3 They can be the same or different.

[0417] In the general formula (B02), X 1 ~X 3 Each independently represents a group represented by the general formula (B2R).

[0418] [Chemical formula 19]

[0419]

[0420] In the general formula (B2R), * indicates 1 ~B 3 The bonding position of any one of them.

[0421] In the general formula (B2R), D 1 It represents a single bond or a divalent linking group.

[0422] Examples of the divalent linking group include -O-, -S-, -CO-, and -NR N -, -SO2-, alkylene and combinations thereof. -NR N -R in N represents a hydrogen atom or a substituent. The alkylene group is preferably a linear or branched alkylene group having 1 to 8 carbon atoms.

[0423] Among them, D 1 Preferably, it is "a single bond" or "a group including a combination selected from the group consisting of -O-, -CO- and an alkylene group", and more preferably, it is a single bond, * A -Alkylene-O-CO-* B ,* A -CO-O-alkylene-* B ,* A -O-Alkylene-O-* B ,* A -CO-O-Alkylene-O-CO-* B ,* A -CO-O-alkylene-O-* B or* A -O-Alkylene-O-CO-* B .

[0424] * A Yes and A 1 Bonding position on the opposite side, * B Yes and A 1 bonding position.

[0425] In the general formula (B2R), A 1 It represents an aromatic ring group which may have a substituent and has 6 or more ring members, that is, carbon atoms, or a cycloalkyl ring group which may have a substituent and has 6 or more ring members, that is, carbon atoms.

[0426] In addition, A 1 Through the ring member atoms of the above aromatic ring group or the above cycloalkyl ring group and D 1 , Y 1 and QB Bonding.

[0427] A 1 The aromatic ring group having 6 or more carbon atoms and B 1 ~B 3 The aromatic ring groups having 6 or more carbon atoms and having a substituent or not are the same.

[0428] A 1 In the cycloalkyl ring group which may have a substituent and has 6 or more carbon atoms as ring member atoms, the cycloalkyl ring group may be a monocyclic ring or a polycyclic ring.

[0429] The monocyclic cycloalkyl ring group preferably has 6 to 10 ring members.

[0430] The number of rings constituting the polycyclic cycloalkyl ring group is preferably 2 to 4, more preferably 2. The number of ring members constituting the polycyclic cycloalkyl ring group is preferably 5 to 10, respectively, independently.

[0431] When the cycloalkane ring group has a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring other than the cycloalkane ring.

[0432] The number of carbon atoms as ring member atoms of the cycloalkyl ring group is 6 or more (preferably 6 to 12). The number of carbon atoms as ring member atoms means the number of carbon atoms as ring member atoms constituting the cycloalkyl ring.

[0433] When a cycloalkyl ring group has a plurality of substituents and the plurality of substituents are bonded to each other to form a ring other than a cycloalkyl ring, the number of carbon atoms contained only in the ring other than the cycloalkyl ring is not counted as the number of carbon atoms as the ring member atoms. In addition, carbon atoms shared by the cycloalkyl ring and the ring other than the cycloalkyl ring in the cycloalkyl ring group are counted as the number of carbon atoms as the ring member atoms.

[0434] As A 1 In the cycloalkyl ring group, which may have a substituent and has 6 or more ring members, that is, carbon atoms, there can be mentioned, for example, a cyclohexyl ring group, a cycloheptyl ring group, a norbornane ring group and an adamantane ring group.

[0435] In the general formula (B2R), Q B and Y 1 Each independently represents a specific functional group selected from the group consisting of an aldehyde group (-CHO), a boronic acid group (-B(OH)2), a hydroxyl group (-OH), a monovalent group having an epoxy group, an amino group, a thiol group (-SH), a carboxylic acid group (-COOH), a monovalent group having a carboxylic anhydride group, an isocyanate group (-NCO) and a monovalent group having an oxetane group.

[0436] That is, the group represented by the general formula (B2R) is a group having at least one specific functional group. The group represented by the general formula (B2R) is a "group having a specific functional group", and the group represented by the general formula (B2R) may be a group containing a specific functional group as a part, or the group represented by the general formula (B2R) may be the specific functional group itself.

[0437] The monovalent group having an epoxy group as the specific functional group is preferably represented by "-L eo -epoxy" represented by the group. eo Preferred are single bonds or divalent linking groups, oxygen atoms, alkylene groups (preferably linear or branched alkylene groups having 1 to 6 carbon atoms), or groups containing a combination thereof.

[0438] Among them, the monovalent group having the above epoxy group is preferably "-O-alkylene-epoxy group".

[0439] The substituent that the epoxy group may have is preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

[0440] The amino group as the specific functional group is not particularly limited, and may be any of primary amino, secondary amino, and tertiary amino. E )2(R E Each independently represents a hydrogen atom or an alkyl group (which may be linear or branched). The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The alkyl group may further have an amino group represented by a substituent).

[0441] Examples of the monovalent group having a carboxylic anhydride group as the specific functional group include groups obtained by removing any hydrogen atoms from maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride.

[0442] The monovalent group having oxetane as the specific functional group is preferably, for example, a group consisting of "-L eo -oxetane" represented by a group. eo Preferred are single bonds or divalent linking groups, oxygen atoms, alkylene groups (preferably linear or branched alkylene groups having 1 to 6 carbon atoms), or groups containing a combination thereof.

[0443] Among them, the monovalent group having oxetane is preferably "-O-alkylene-oxetane group".

[0444] The substituent that the oxetanyl group may have is preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

[0445] Among them, the specific functional group is preferably an aldehyde group, a boric acid group, a hydroxyl group, or a monovalent group having an epoxy group.

[0446] In other words, Q B and Y 1 Each of them is independently preferably an aldehyde group, a boronic acid group, a hydroxyl group or a monovalent group having an epoxy group.

[0447] In the general formula (B2R), p represents an integer of 0 or more.

[0448] Among them, p is preferably 0-5, more preferably 0-1.

[0449] When p is 0, Y 1 With B 1 ~B 3 Any one of them is directly bonded. That is, X 1 ~X 3 It may be a specific functional group itself.

[0450] In the general formula (B2R), q represents an integer of 0-2.

[0451] Among them, q is preferably 0-1.

[0452] When there are plural groups represented by the general formula (B2R) in the compound represented by the general formula (B02), the plural groups represented by the general formula (B2R) may be the same or different.

[0453] For example, in the general formula (B2R), D 1 When there are multiple, there are multiple D 1 They can be the same or different. 1 When there are multiple A 1 They can be the same or different. B When there are multiple, there are multiple Q B They can be the same or different. 1 When there are multiple, there are multiple Y 1 When there are multiple p, the two or more p's may be the same or different. When there are multiple q's, the multiple q's may be the same or different.

[0454] In the general formula (B02), the total number of lb, mb and nb is 2 or more (preferably 2 to 10, more preferably 3 to 6).

[0455] In other words, there can be multiple X 1 ~X 3 The total number of is 2 or more (preferably 2 to 10, more preferably 3 to 6).

[0456] That is, in the general formula (B02), there may be a plurality of X 1 The number of Xs that can exist 2 The number of Xs and the number of Xs that can exist 3 The total number of is 2 or more, preferably 2 to 10, more preferably 3 to 6.

[0457] For example, lb is preferably 1 or more (more preferably 1 to 2), mb is preferably 1 or more (more preferably 1 to 2), and nb is preferably 1 or more (more preferably 1 to 2).

[0458] That is, B 1 It is preferred to have one or more (more preferably 1 to 2) X 1 , B 2 It is preferred to have one or more (more preferably 1 to 2) X 2 , B 3 It is preferred to have one or more (more preferably 1 to 2) X 3 .

[0459] Where lb is greater than 1 and at least 1 X 1 When it is a hydroxyl group, it is preferably the above-mentioned hydroxyl group, that is, X 1 Directly bonded B 1 The atoms in E 1 Directly bonded B 1 The atoms in the molecule are not adjacent to each other.

[0460] mb is 1 or more, at least 1 X 2 When it is a hydroxyl group, it is preferably the above-mentioned hydroxyl group, that is, X 2 Directly bonded B 2 The atoms in E 2 Directly bonded B 2 The atoms in the molecule are not adjacent to each other.

[0461] nb is greater than 1, at least 1 X 3 When it is a hydroxyl group, it is preferably the above-mentioned hydroxyl group, that is, X 3 Directly bonded B 3 The atoms in E 3 Directly bonded B 3 The atoms in the molecule are not adjacent to each other.

[0462] For example, in B 1 In the case of a benzene ring group, the above-mentioned benzene ring group is 1 When there is a hydroxyl group at the ortho position of X 1 , can be excluded from the above "there can be multiple X 1 of”.

[0463] The inventors believe that B1 ~B 3 on, existing in and with E 1 ~E 3 Hydroxyl groups at adjacent positions are greatly affected by steric hindrance effects, and it is difficult to form a good thermal conductivity path between inorganic substances (inorganic nitrides, etc.). However, hydroxyl groups at different positions have a better effect of improving thermal conductivity.

[0464] For example, E 1 Directly bonded B 1 The atoms in the adjacent B 1 The atoms (preferably carbon atoms) in E are preferably unsubstituted. 2 Directly bonded B 2 The atoms in the adjacent B 2 The atoms (preferably carbon atoms) in E are preferably unsubstituted. 3 Directly bonded B 3 The atoms in the adjacent B 3 The atoms (preferably carbon atoms) in are preferably unsubstituted.

[0465] The compound represented by the general formula (B02) may have one type of group represented by the general formula (B2R) alone, or may have two or more types.

[0466] Among them, the compound represented by the general formula (B02) is preferably a "compound having only a hydroxyl group as a specific functional group", "a compound having only a monovalent epoxy group as a specific functional group" or "a compound having a group that is not an aldehyde group or a boronic acid group (preferably a hydroxyl group) and an aldehyde group and / or a boronic acid group as a specific functional group".

[0467] In addition, as the above-mentioned "compound having a group which is not an aldehyde group or a boronic acid group and two specific functional groups, an aldehyde group and / or a boronic acid group", for example, a compound wherein in the compound represented by the general formula (B02), there are 1 b X 1 , there are mb X 2 And there are nb X 3 In (i.e., among the groups represented by the general formula (B2R) that exist in lb+mb+nb numbers), at least one in total is a group having at least one specific functional group among an aldehyde group and a boronic acid group, and

[0468] There are lb X 1 , there are mb X 2 And there are nb X 3In the group (that is, among the groups represented by the general formula (B2R) that exist in lb+mb+nb numbers), a total of one or more (preferably 1 to 4) are groups having a specific functional group that is neither an aldehyde group nor a boronic acid group.

[0469] The above-mentioned “group having at least one specific functional group of an aldehyde group and a boronic acid group” and the above-mentioned “group having a specific functional group which is neither an aldehyde group nor a boronic acid group” preferably exist as independent groups.

[0470] The above-mentioned “specific functional group which is neither an aldehyde group nor a boronic acid group” is preferably a hydroxyl group or a monovalent group having an epoxy group, and more preferably a hydroxyl group.

[0471] The above-mentioned “group having at least one specific functional group of an aldehyde group and a boronic acid group” also preferably does not have any of the “specific functional groups which are not either an aldehyde group or a boronic acid group”.

[0472] Furthermore, the above-mentioned “group having a specific functional group which is neither an aldehyde group nor a boronic acid group” also preferably does not have either an aldehyde group nor a boronic acid group.

[0473] By satisfying such conditions, the thermal conductivity of the obtained thermally conductive material is further improved. The present inventors speculate the following mechanism.

[0474] That is, when the compound represented by the general formula (B02) has an aldehyde group and / or a boronic acid group as a specific functional group, the aldehyde group and / or the boronic acid group interacts particularly well with an inorganic substance (especially an inorganic nitride such as boron nitride).

[0475] When the compound represented by the general formula (B02) further has other specific functional groups in addition to the aldehyde group and / or the boronic acid group, the aldehyde group and / or the boronic acid group mainly interact with the inorganic substance (especially the inorganic nitride), and on the other hand, the above-mentioned other specific functional groups also form a heat conduction path based on interaction with substances other than the inorganic substance (for example, between the compounds represented by the general formula (B02)), and the thermal conductivity of the obtained thermally conductive material is more excellent. In addition, it is speculated that the above-mentioned other specific functional groups sometimes form an interaction based on chemical bonding with a resin including a phenol compound and / or an epoxy compound (a compound represented by the general formula (1) or the like), and in this case, the thermal conductivity of the obtained thermally conductive material is more excellent.

[0476] (Compound represented by general formula (B03))

[0477] Among them, the compound represented by the general formula (B02) is preferably a compound represented by the general formula (B03).

[0478] [Chemical formula 20]

[0479]

[0480] In the general formula (B03), E 1 ~E 3 Each independently represents a single bond, -NH- or -NR-. R represents a substituent.

[0481] E in the general formula (B03) 1 ~E 3 With E in the general formula (B02) 1 ~E 3 same.

[0482] In the general formula (B03), g 1 ~g 3 Each independently represents an integer of 0 or 1.

[0483] In the general formula (B03), Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c Each independently represents a hydrogen atom or a group represented by the general formula (B2R).

[0484] Among them, Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c In the above, a total of 2 or more (preferably 2 to 9, more preferably 3 to 6) groups are groups represented by the general formula (B2R).

[0485] The group represented by the general formula (B2R) is as described above.

[0486] Preferably Z 1a ~Z 1c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (B2R), and Z 2a ~Z 2c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (B2R), and Z 3a ~Z 3c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (B2R).

[0487] Among them, Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3cEach of them is independently preferably "a group selected from the group of groups represented by the general formula (B2R) including a hydrogen atom and a specific functional group being a hydroxyl group", or "a group selected from the group of groups represented by the general formula (B2R) including a hydrogen atom and a specific functional group being a monovalent group having an epoxy group".

[0488] In addition, Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c In the formula (B2R), at least one (preferably 1 to 2) of the esters are groups having at least one specific functional group of an aldehyde group and a boronic acid group, and

[0489] In Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c It is also preferred that at least one (preferably 1 to 4) of the groups be a group represented by the general formula (B2R) having a specific functional group which is neither an aldehyde group nor a boronic acid group.

[0490] Among them, Z 1a ~Z 1c One or more (preferably 1 to 2) of the above are groups represented by the general formula (B2R) having at least one specific functional group of an aldehyde group and a boronic acid group,

[0491] Z 2a ~Z 2c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (B2R) having a specific functional group that is not an aldehyde group or a boronic acid group, and

[0492] Z 3a ~Z 3c More preferably, one or more (preferably 1 to 2) of the groups are groups represented by the general formula (B2R) having a specific functional group that is neither an aldehyde group nor a boronic acid group.

[0493] The above-mentioned “specific functional group which is neither an aldehyde group nor a boronic acid group” is preferably a hydroxyl group or a monovalent group having an epoxy group, and more preferably a hydroxyl group.

[0494] The above-mentioned “group represented by the general formula (B2R) having a specific functional group which is not an aldehyde group or a boronic acid group” also preferably has no “specific functional group which is not an aldehyde group or a boronic acid group”.

[0495] Furthermore, the above-mentioned “group represented by the general formula (B2R) having a specific functional group which is neither an aldehyde group nor a boronic acid group” also preferably has neither an aldehyde group nor a boronic acid group.

[0496] <Other surface modifiers (surface modifiers for inorganic oxides)>

[0497] In addition, the composition also preferably contains (preferably when the inorganic substance contains an inorganic oxide (aluminum oxide, etc.)) an organosilane molecule (preferably a compound having an alkoxysilyl group) as a surface modifier. Examples of the above-mentioned organosilane molecule include other surface modifiers that do not correspond to either of the surface modifier A and the surface modifier B.

[0498] The organosilane molecule as such another surface modifier is preferably used as a surface modifier for an inorganic oxide (preferably a surface modifier for alumina).

[0499] As the organic silane molecules of the above-mentioned other surface modifiers, for example, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane and 3-ureapropyltriethoxysilane can be mentioned.

[0500] The surface modifier may be used alone or in combination of two or more.

[0501] When the composition contains a surface modifier (preferably a surface modifier for inorganic nitrides and / or inorganic oxides), the content of the surface modifier is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the composition.

[0502] The content of the inorganic nitride surface modifier (preferably the total content of the surface modifier A and the surface modifier B) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the composition.

[0503] The content of the inorganic oxide surface modifier (preferably an organosilane molecule as another surface modifier) ​​is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the composition.

[0504] When the composition contains a surface modifier (preferably a surface modifier for inorganic nitrides and / or inorganic oxides), the content of the surface modifier is preferably 0.01 to 10 mass %, more preferably 0.10 to 5 mass % based on the total mass of the inorganic substance.

[0505] The content of the inorganic nitride surface modifier (preferably the total content of the surface modifier A and the surface modifier B) is preferably 0.01 to 10% by mass, more preferably 0.10 to 5% by mass, relative to the total mass of the inorganic nitride (preferably boron nitride).

[0506] The content of the inorganic oxide surface modifier (preferably an organosilane molecule as another surface modifier) ​​is preferably 0.01 to 10% by mass, more preferably 0.10 to 5% by mass, based on the total mass of the inorganic oxide (preferably alumina).

[0507] In the composition of the present invention, the ratio of the total number of phenolic hydroxyl groups possessed by the solid component (for example, the total number of phenolic hydroxyl groups possessed by the phenol compound represented by the general formula (1), the total number of phenolic hydroxyl groups possessed by other phenolic compounds and the total number of phenolic hydroxyl groups possessed by the surface modifier having a phenolic hydroxyl group) to the total number of epoxy groups possessed by the solid component (for example, the total number of epoxy groups possessed by the epoxy compound and the total number of epoxy groups possessed by the surface modifier having an epoxy group) (total number of phenolic hydroxyl groups possessed by the solid component / total number of epoxy groups possessed by the solid component) is preferably 0.50 to 2.00, more preferably 0.65 to 1.50, and further preferably 0.90 to 1.10.

[0508] In the composition of the present invention, the ratio of the total number of active hydrogen atoms (hydrogen atoms of phenolic hydroxyl groups, etc.) possessed by the solid component to the total number of epoxy groups possessed by the solid component (total number of active hydrogen atoms possessed by the solid component / total number of epoxy groups possessed by the solid component) is preferably 0.50 to 2.00, more preferably 0.65 to 1.50, and further preferably 0.90 to 1.10.

[0509] 〔Curing accelerator〕

[0510] The composition may also contain a curing accelerator.

[0511] Examples of the curing accelerator include triphenylphosphine, boron trifluoride amine complex, and the compounds described in paragraph 0052 of JP-A-2012-67225. In addition, 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name; 1.2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl-2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl-2-phenylimidazole trimellitic acid (trade name; 2PZCNS-PW), 2,4-diamino-6-[2'-methyl Imidazole-(1')]-ethyl-s-triazine (trade name: 2MZ-A), 2,4-diamino-6-[2'-undecylimidazole-(1')]-ethyl-s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazole-(1')]-ethyl-s-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazole-(1')]-ethyl-s-triazine )]-ethyl-s-triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethylimidazole (trade name; 2P4MHZ-PW) and 1-cyanoethyl-2-phenylimidazole (trade name; 2PZ-CN) and other imidazole curing accelerators (all manufactured by SHIKOKU CHEMICALS CORPORATION).

[0512] The curing accelerator may be used alone or in combination of two or more.

[0513] When the composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total content of the phenol compound (the phenol compound represented by the general formula (1) and other phenol compounds) and the epoxy compound.

[0514] 〔Dispersant〕

[0515] The composition may also contain a dispersant.

[0516] When the composition contains a dispersant, the dispersibility of the inorganic substance in the composition is improved, and more excellent thermal conductivity and adhesiveness can be achieved.

[0517] The dispersant may be appropriately selected from commonly used dispersants, for example, DISPERBYK-106 (manufactured by BYK-Chemie GmbH), DISPERBYK-111 (manufactured by BYK-Chemie GmbH), ED-113 (manufactured by Kusumoto Chemicals, Ltd.), Addispar PN-411 (manufactured by Ajinomoto Fine-Techno Co., Inc.), and REB122-4 (manufactured by Hitachi Chemical Co., Ltd.).

[0518] The dispersants may be used alone or in combination of two or more.

[0519] When the composition contains a dispersant, the content of the dispersant is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the content of the inorganic substance.

[0520] 〔Solvent〕

[0521] The composition may also contain a solvent.

[0522] The type of solvent is not particularly limited, but an organic solvent is preferred. Examples of the organic solvent include cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane, and tetrahydrofuran.

[0523] When the composition contains a solvent, the content of the solvent is such that the solid content concentration of the composition is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and even more preferably 40 to 85% by mass.

[0524] [Method for producing the composition]

[0525] The method for producing the composition is not particularly limited, and a known method can be used. For example, the composition can be produced by mixing the above-mentioned various components. When mixing, the various components can be mixed at once or sequentially.

[0526] The method of mixing the components is not particularly limited, and known methods can be used. The mixing device for mixing is preferably a liquid disperser, and for example, a mixer such as a rotation-revolution mixer, a high-speed rotary shearing mixer, a rubber mill, a roller mill, a high-pressure jet disperser, an ultrasonic disperser, a bead mill, and a homogenizer can be cited. The mixing device can be used alone or in combination. Degassing can be performed before, after, and / or simultaneously with the mixing.

[0527] [Method for curing the composition]

[0528] The composition of the present invention is preferably a composition for forming a thermally conductive material.

[0529] The thermally conductive material can be obtained by curing the composition of the present invention.

[0530] The curing method of the composition is not particularly limited, but thermal curing reaction is preferred.

[0531] The heating temperature during the thermal curing reaction is not particularly limited and may be appropriately selected within the range of 50 to 250° C. Furthermore, during the thermal curing reaction, a plurality of heating treatments at different temperatures may be performed.

[0532] The curing treatment is preferably performed on the composition in the form of a film or a sheet. Specifically, for example, the composition may be applied to form a film and then subjected to a curing reaction.

[0533] When performing the curing treatment, it is preferred to apply the composition on the substrate to form a coating film and then cure it. At this time, different substrates can also be further contacted with the coating film formed on the substrate before performing the curing treatment. The cured product (thermal conductive material) obtained after curing can be separated from one or both sides of the substrate, or it can be not separated.

[0534] Furthermore, when performing the curing treatment, the composition may be applied on separate substrates to form coatings, and the coatings obtained may be cured while being in contact with each other. The cured product (thermal conductive material) obtained after curing may be separated from one or both sides of the substrate, or may not be separated.

[0535] During the curing process, extrusion processing can be performed. There is no limitation on the extrusion used for the extrusion processing, for example, flat plate extrusion or roller pressing can be used.

[0536] When roller pressing is used, for example, it is preferred that a substrate with a film formed on a substrate is sandwiched between a pair of rollers opposed to each other, and pressure is applied in the film thickness direction of the substrate with a film while the pair of rollers are rotated to pass the substrate with the film. The substrate with a film may exist only on one side of the coating film, or on both sides of the coating film. The substrate with a film may pass through the roller pressing only once, or may pass through multiple times.

[0537] Only one of the flat plate pressing process and the roller pressing process may be performed, or both of them may be performed.

[0538] Furthermore, the curing treatment may be terminated when the composition is in a semi-cured state. The semi-cured thermal conductive material of the present invention may be placed in contact with a device to be used, and then further cured by heating or the like, thereby making it fully cured. It is also preferred that the device and the thermal conductive material of the present invention be bonded by heating or the like during the above-mentioned full curing.

[0539] Regarding the preparation of the thermally conductive material including the curing reaction, reference can be made to "High Thermal Conductivity Composite Material" (published by CMC, written by Takezawa Yutaka).

[0540] The shape of the heat conductive material is not particularly limited, and it can be formed into various shapes according to the application. A typical shape of the formed heat conductive material is, for example, a sheet shape.

[0541] That is, the thermally conductive material obtained using the composition of the present invention is also preferably a thermally conductive sheet.

[0542] Furthermore, the thermal conductivity of the thermally conductive material obtained using the composition of the present invention is preferably isotropic rather than anisotropic.

[0543] The thermally conductive material is preferably insulating (electrically insulating). In other words, the composition of the present invention is preferably a thermally conductive insulating composition.

[0544] For example, the volume resistivity of the thermally conductive material at 23°C and 65% relative humidity is preferably 10 10 Ω·cm or more, more preferably 10 12 Ω·cm or more, more preferably 10 14 Ω·cm or more. The upper limit is not particularly limited, but is usually 10 18 Ω·cm or less.

[0545] [Application of thermal conductive materials]

[0546] The thermally conductive material obtained by using the composition of the present invention can be used as a heat dissipation material such as a heat sink, and can be used for heat dissipation of various devices. More specifically, a device with a thermally conductive layer is prepared by configuring a thermally conductive layer containing the thermally conductive material of the present invention on a device, thereby effectively dissipating heat generated by the device using the thermally conductive layer.

[0547] The thermally conductive material obtained by using the composition of the present invention has sufficient thermal conductivity and high heat resistance, and is therefore suitable for heat dissipation of power semiconductor devices used in various electrical equipment such as personal computers, general household appliances, and automobiles.

[0548] Furthermore, the thermally conductive material obtained using the composition of the present invention has sufficient thermal conductivity even in a semi-cured state, and can therefore be used as a heat dissipation material disposed in locations where light used for photocuring is difficult to reach, such as gaps between components of various devices. In addition, since it has excellent adhesiveness, it can also be used as a thermally conductive adhesive.

[0549] The thermally conductive material obtained using the composition of the present invention may be used in combination with another member other than the member formed from the present composition.

[0550] For example, a sheet-shaped thermally conductive material (thermally conductive sheet) may be combined with a sheet-shaped support other than the layer formed of the present composition.

[0551] As the sheet-like support, for example, a plastic film, a metal film or a glass plate can be cited. As the material of the plastic film, for example, polyesters such as polyethylene terephthalate (PET), polycarbonate, acrylic resin, epoxy resin, polyurethane, polyamide, polyolefin, cellulose derivatives and polysilicone can be cited. As the metal film, for example, a copper film can be cited.

[0552] The film thickness of the sheet-shaped thermally conductive material (thermal conductive sheet) is preferably 100 to 300 μm, more preferably 150 to 250 μm.

[0553] Example

[0554] Below, the present invention is further described in detail according to the examples. The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the examples shown below.

[0555] 〔Preparation and evaluation of compositions〕

[0556] [Various ingredients]

[0557] Various components used in Examples and Comparative Examples are shown below.

[0558] <Phenol compounds>

[0559] The phenol compounds used in Examples and Comparative Examples are shown below.

[0560] The following phenol compounds A-1 to A-13 are phenol compounds represented by the general formula (1).

[0561] In the following phenol compounds, Mn represents the number average molecular weight of the phenol compound. The phenol compound having the number average molecular weight described is a mixture of compounds having different values ​​only in n. n represents an integer greater than or equal to 0.

[0562] [Chemical formula 21]

[0563]

[0564] [Chemical formula 22]

[0565]

[0566] (Synthesis Example A-1)

[0567] Phenol compound A-1 was obtained by the following method.

[0568] In a flask, 30 g of monomer pyrogallol as a phenol compound and 100 g of water as a solvent were mixed and stirred. In the above flask, 0.6 g of oxalic acid and 14.5 g of 37% by mass formaldehyde water as a catalyst were further added, and stirred at 105°C for 4 hours. After the contents of the above flask were cooled to room temperature, the slurry obtained in the flask was filtered to obtain a crude product (filtrate) of the phenol compound. The obtained crude product was dissolved in 200 g of acetone, and the insoluble matter was removed by diatomaceous earth filtration. Under reduced pressure, acetone was distilled off from the filtrate, and after adding water to obtain slurry again, the slurry was filtered to obtain a phenol compound A-1 (filtrate).

[0569] (Synthesis Example A-2)

[0570] A phenol compound A-2 was obtained by the same method as in Synthesis Example A-1 except that the added amount of 37 mass % formalin water was 12.9 g.

[0571] (Synthesis Example A-3)

[0572] In a flask, 5 g of 3,4,5-trihydroxybenzaldehyde, 30 g of pyrogallol and 40 ml of ethanol were mixed. The contents of the flask were cooled to 0°C, and 12 ml of a 1 / 1 mixed solution of concentrated sulfuric acid / ethanol (mass ratio) was added dropwise to the flask. After that, the contents of the flask were reacted at room temperature for 12 hours, and the obtained reaction solution was separated with a mixed solution of ethyl acetate / THF (tetrahydrofuran) and water, and the reaction product in the reaction solution was extracted into an organic phase. The solvent was distilled off from the organic phase, and purified by column chromatography to obtain phenol compound A-3.

[0573] (Synthesis Examples A-4 to A-13)

[0574] Referring to Synthesis Example A-3, phenol compounds A-4 to A-13 were obtained.

[0575] <Epoxy compounds>

[0576] The epoxy compounds used in Examples and Comparative Examples are shown below.

[0577] In addition, the epoxy compound B-2 is a mixture of two epoxy compounds (trade name: Epotote ZX-1059, manufactured by Tohto Kasei Co., Ltd.).

[0578] [Chemical formula 23]

[0579]

[0580] <Inorganic substances (inorganic nitrides and inorganic oxides)>

[0581] Inorganic substances used in Examples and Comparative Examples are shown below.

[0582] "AA-3": Alumina (average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd.)

[0583] "AA-04": Alumina (average particle size: 0.4 μm, manufactured by Sumitomo Chemical Co., Ltd.)

[0584] “HP-40MF100”: Agglomerated boron nitride (average particle size: 40 μm, manufactured by Mizushima Ferroalloy Co., Ltd.)

[0585] <Curing accelerator>

[0586] The curing accelerators used in Examples and Comparative Examples are shown below.

[0587] "E-1": PPh3 (triphenylphosphine)

[0588] "E-2": 1-cyanoethyl-2-phenylimidazole (trade name; 2PZ-CN, manufactured by SHIKOKU CHEMICALS CORPORATION)

[0589] “E-3”: 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW, manufactured by SHIKOKU CHEMICALS CORPORATION)

[0590] <Dispersant>

[0591] As the dispersant, DISPERBYK-106 (polymer salt having an acidic group) was used.

[0592] <Surface Modifier>

[0593] As the surface modifier for inorganic nitride, the following compounds were used.

[0594] [Chemical formula 24]

[0595]

[0596] As the surface modifier (organosilane molecule) for aluminum oxide, the following compounds were used.

[0597] [Chemical formula 25]

[0598]

[0599] <Solvent>

[0600] As the solvent, cyclopentanone was used.

[0601] [Preparation of composition]

[0602] Curing solutions of epoxy compounds and phenol compounds in the combinations shown in Table 1 below were prepared.

[0603] After the total amount of the obtained solidified liquid, the solvent, the dispersant, the surface modifier (surface modifier for alumina, surface modifier for inorganic nitride) and the curing accelerator were mixed in sequence, the inorganic substance (inorganic nitride, inorganic oxide) was added. The obtained mixture was treated for 5 minutes using a rotation-revolution mixer (manufactured by THINKY Co., Ltd., Awatori NetaroARE-310), thereby obtaining the composition (composition for forming a thermally conductive material) of each example or comparative example.

[0604] However, the amount of the solvent added is set to an amount such that the solid content concentration of the composition becomes 50 to 80% by mass.

[0605] In addition, the solid content concentration of the composition was adjusted within the above range for each composition so that the viscosity of the composition would be approximately the same.

[0606] In addition, the inorganic substances are mixed so that the content ratio (mass ratio) of each inorganic substance satisfies the relationship shown in Table 1 and used.

[0607] Table 1 shows the composition of the solid content in each example or comparative example.

[0608] [evaluate]

[0609] <Thermal conductivity>

[0610] The prepared composition was uniformly applied on a release surface of a release-treated polyester film (NP-100 manufactured by APANAC Co., Ltd., film thickness 100 μm) using an applicator and allowed to stand at 120° C. for 5 minutes to obtain a coating film.

[0611] Two sheets of such coated polyester films were prepared, and the coated surfaces of the two coated polyester films were bonded to each other, and then hot pressed in air (treated at a hot plate temperature of 65°C and a pressure of 12 MPa for 1 minute), thereby obtaining a semi-cured film. The obtained semi-cured film was treated by hot pressing in air (treated at a hot plate temperature of 160°C and a pressure of 12 MPa for 20 minutes, and then further treated at 180°C for 90 minutes under normal pressure) to cure the coated film, thereby obtaining a resin sheet. The polyester films on both sides of the resin sheet were peeled off, thereby obtaining a thermally conductive sheet (sheet-shaped thermally conductive material) with an average film thickness of 200 μm.

[0612] Thermal conductivity evaluation was performed on each thermally conductive sheet obtained using each composition. Thermal conductivity was measured using the following method, and thermal conductivity was evaluated based on the following criteria.

[0613] (Measurement of thermal conductivity (W / m·k))

[0614] (1) The thermal diffusivity in the thickness direction of the thermally conductive sheet was measured by a laser flash method using "LFA467" manufactured by NETZSCH.

[0615] (2) The specific gravity of the thermally conductive sheet was measured by the Archimedean method using a balance "XS204" manufactured by METTLER TOLEDO (using a "solid specific gravity measurement kit").

[0616] (3) The specific heat of the thermally conductive sheet at 25° C. was determined using “DSC320 / 6200” manufactured by Seiko Instruments Inc. under the temperature increase condition of 10° C. / min.

[0617] (4) The thermal conductivity of the thermally conductive sheet is calculated by multiplying the obtained thermal diffusivity by the specific gravity and specific heat.

[0618] (Evaluation Criteria)

[0619] The measured thermal conductivities were classified according to the following criteria and used as thermal conductivity evaluation.

[0620] "A+": 15W / m·K or above

[0621] "A": 10W / m·K or more and less than 15W / m·K

[0622] "B": 8W / m·K or more and less than 10W / m·K

[0623] "C": 5W / m·K or more and less than 8W / m·K

[0624] "D": less than 5W / m·K

[0625] Table 1 shows the results.

[0626] <Insulation>

[0627] The thermally conductive sheet produced in the same manner as in the above-mentioned evaluation of "thermal conductivity" was measured for volume resistivity at 23° C. and a relative humidity of 65% using Hiresta MCP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

[0628] (Evaluation Criteria)

[0629] The measured volume resistance values ​​of the thermally conductive sheets were classified according to the following criteria, and the insulation properties were evaluated.

[0630] "A": 10 14 Ω·cm or more

[0631] "B": 10 12 Ω·cm or more and less than 10 14 Ω·cm

[0632] "C": 10 10 Ω·cm or more and less than 10 12 Ω·cm

[0633] "D": less than 10 10 Ω·cm

[0634] <Adhesion>

[0635] Copper plates were used as adherends and the composition was used as an adhesive, and a tensile shear test according to JIS K6850 was carried out.

[0636] Separately, a test piece was prepared by bonding two copper plates (size: 100 mm×25 mm×0.3 mm) to a bonding area of ​​12.5 mm×25 mm.

[0637] The curing conditions of the composition were set to be the same as those used in producing the thermally conductive sheet in the thermal conductivity measurement.

[0638] A TENSILON universal material testing machine RTc-1225A was used in the test, and the tensile rate was set to 0.05 mm / s.

[0639] (Evaluation Criteria)

[0640] The measured breaking stress was classified according to the following criteria, and the adhesiveness was evaluated.

[0641] "A": 5MPa or more

[0642] "B": 4MPa or more and less than 5MPa

[0643] "C": less than 4MPa

[0644] [result]

[0645] Table 1 is shown below.

[0646] In Table 1, the column "Content (%)" shows the content (mass %) of each component relative to the total solid content.

[0647] The column "p" shows the value of p when the phenol compound in the composition of the example is introduced into the general formula (1).

[0648] The column "q" shows the value of q when the phenol compound in the composition of the example is introduced into the general formula (1). However, when the phenol compound does not have a group represented by the general formula (2), it is described as "-".

[0649] The column "p+q" indicates the total value of the above "p" and "q". However, when the phenol compound does not have a group represented by the general formula (2), it is indicated as "-".

[0650] [Table 1]

[0651]

[0652]

[0653]

[0654]

[0655] From the results shown in the table, it was confirmed that the composition of the present invention can provide a thermally conductive material having excellent thermal conductivity. In addition, it was confirmed that the thermally conductive material also has excellent insulation and adhesive properties.

[0656] Furthermore, it was confirmed that when p in the general formula (1) is 3 or more, the thermal conductivity of the obtained thermally conductive material is more excellent.

[0657] (Results of Examples 37 to 52, etc.)

[0658] It was confirmed that when the number average molecular weight of the phenol compound represented by the general formula (1) is 420 or less, the thermal conductivity or adhesiveness of the obtained thermally conductive material is more excellent.

[0659] (Comparison between Examples 1 to 4, 25 to 28 and Examples 5 to 24, 29 to 36 (Comparison between conditions where p ≥ 3 in the general formula (1)), Comparison between Examples 37 to 44 and Examples 45 to 48 (Comparison between conditions where p = 2 and p + q ≥ 4 in the general formula (1)), etc.)

[0660] Furthermore, it was confirmed that in the general formula (1), R 1 ~R 3 When at least one of the groups is a group represented by the general formula (2), when p+q is an integer of 4 or more, the adhesiveness of the obtained thermally conductive material is more excellent.

[0661] (Comparison between Examples 37 to 44 and Examples 49 to 52 (Comparison between the conditions where p=2 in the general formula (1) and the number average molecular weight is 420 or less) etc.)

[0662] It was confirmed that when the content of the inorganic nitride in the composition is 50% by mass or more relative to the total mass of the inorganic substance, the thermal conductivity of the obtained thermally conductive material is more excellent.

[0663] (Comparison of Examples 77 to 80 with Examples 9 to 12, etc.)

[0664] It was confirmed that when the composition contains a surface modifier for inorganic nitrides, the thermal conductivity of the obtained thermally conductive material is more excellent. (Comparison of Examples 41 to 44 with Examples 61 to 68, etc.)

Claims

1. A composition for forming a thermally conductive material, comprising a phenol compound represented by the general formula (1), an epoxy compound and an inorganic substance, [Chemical formula 1] In the general formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group which may be substituted, an aralkyl group which may be substituted, or a group represented by the general formula (2), in, When R 1 and R 2 When one of them represents a hydrogen atom, the other represents a group represented by the general formula (2), and the total of q+k in the general formula (2) represents an integer of 1 to 5. R 3 represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a group represented by the general formula (2), n represents an integer greater than 0, j represents 0, p represents an integer greater than or equal to 2, Among them, -(R 3 The value of j+p in -(OH)p is an integer from 2 to 4. [Chemical formula 2] In the general formula (2), * indicates the bonding position, R 4 represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, k represents an integer greater than 0, q represents an integer greater than 0, Wherein, k+q is an integer from 0 to 5, When there are two or more R in the general formula (1), or when there are not two or more R 1 ~R 3 When all represent a group other than the group represented by the general formula (2) in which q is an integer of 1 or more, in the general formula (1), p is an integer of 3 or more.

2. A composition for forming a thermally conductive material, comprising a phenol compound represented by the general formula (1), an epoxy compound and an inorganic substance, [Chemical formula 1] In the general formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group which may be substituted, an aralkyl group which may be substituted, or a group represented by the general formula (2), R 3 represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a group represented by the general formula (2), n represents an integer from 1 to 5, j represents 0, p represents an integer greater than or equal to 2, in, -(R 3 The value of j+p in -(OH)p is an integer from 2 to 4. [Chemical formula 2] In the general formula (2), * indicates the bonding position, R 4 represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, k represents an integer greater than 0, q represents an integer greater than 0, Wherein, k+q is an integer from 0 to 5, When there are two or more R in the general formula (1), or when there are not two or more R 1 ~R 3 When all represent a group other than the group represented by the general formula (2) in which q is an integer of 1 or more, in the general formula (1), p is an integer of 3 or more.

3. The thermally conductive material forming composition according to claim 1 or 2, wherein p represents an integer of 3 or more.

4. The thermally conductive material forming composition according to claim 1 or 2, wherein The number average molecular weight of the phenol compound represented by the general formula (1) is 420 or less.

5. The thermally conductive material forming composition according to claim 1 or 2, wherein When there are two or more R 1 ~R 3 When at least one of the groups is a group represented by the general formula (2), the sum of the average value of p when two or more of the groups exist and the average value of q when two or more of the groups exist or do not exist is 4 or more.

6. The thermally conductive material forming composition according to claim 1 or 2, wherein The epoxy compound has an epoxy group content of 4.0 mmol / g or more.

7. The thermally conductive material forming composition according to claim 1 or 2, wherein The inorganic substance includes an inorganic nitride.

8. The thermally conductive material forming composition according to claim 7, wherein The inorganic nitride includes boron nitride.

9. The thermally conductive material forming composition according to claim 7, wherein The content of the inorganic nitride is 50 mass % or more relative to the total mass of the inorganic substance. 10 . The thermally conductive material forming composition according to claim 7 , further comprising a surface modifier for the inorganic nitride. The thermally conductive material-forming composition according to claim 1 or 2, further comprising a curing accelerator. 12 . A thermally conductive material obtained by curing the thermally conductive material-forming composition according to claim 1 .

Images