Composition, thermal conductive sheet, and device with thermal conductive layer

Abstract

The present invention provides a composition of a thermally conductive material that can impart excellent thermal conductivity. Also, a thermally conductive sheet and a device with a thermally conductive layer are provided. The composition comprises an inorganic nitride and a compound represented by the general formula (1).

Description

Technical Field

[0001] The invention relates to a composition, a heat-conducting sheet and a device with a heat-conducting layer. Background Art

[0002] In recent years, power semiconductor devices used in various electronic devices such as personal computers, general household appliances, and automobiles have been rapidly miniaturized. As miniaturization progresses, it becomes difficult to control the heat generated by the high-density power semiconductor devices.

[0003] To address this problem, thermally conductive materials are used that promote heat dissipation from power semiconductor devices.

[0004] For example, Patent Document 1 discloses “a surface-modified inorganic material in which an inorganic nitride or an inorganic oxide is surface-modified using a boric acid compound ([Claim 1])”.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2016 / 084873 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] The present inventors have studied a thermally conductive material including a surface-modified inorganic substance 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 imparting excellent thermal conductivity to a thermally conductive material.

[0011] Furthermore, another object of the present invention is to provide a thermally conductive sheet and a device with a thermally conductive layer formed from the above composition.

[0012] Means for solving technical problems

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

[0014] [1]

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

[0016] [2]

[0017] The composition as described in [1], wherein in the general formula (2) described below, Q and Y 1Each independently represents a group selected from the group consisting of an aldehyde group, a boronic acid group, a hydroxyl group, and a monovalent group having an epoxy group.

[0018] 〔3〕

[0019] The composition as described in [1] or [2], wherein in the general formula (1) described below, E 1 ~E 3 It represents -NH-.

[0020] [4]

[0021] The composition as described in any one of [1] to [3], further comprising an epoxy compound.

[0022] 〔5〕

[0023] The composition as described in [4], wherein the epoxy compound has an epoxy group content of 4.0 mmol / g or more.

[0024] [6]

[0025] The composition as described in any one of [1] to [5], further comprising a phenol compound.

[0026] 〔7〕

[0027] The composition as described in [6], wherein the hydroxyl content of the above-mentioned phenol compound is 8.0 mmol / g or more.

[0028] 〔8〕

[0029] The composition as described in any one of [1] to [7], further comprising a curing accelerator.

[0030] 〔9〕

[0031] The composition as described in any one of [1] to [8], wherein the inorganic nitride is boron nitride.

[0032] 〔10〕

[0033] A composition as described in any one of [1] to [9], wherein the composition further comprises other inorganic substances other than the inorganic nitride, and the total content of the inorganic nitride and the other inorganic substances is 70 to 85% by mass relative to the total solid content of the composition, or, the composition does not comprise the other inorganic substances, and the content of the inorganic nitride is 70 to 85% by mass relative to the total solid content of the composition.

[0034]

[11]

[0035] The composition according to any one of [1] to

[10] , which is a composition for forming a thermally conductive material.

[0036]

[12]

[0037] A thermally conductive sheet formed by curing the composition described in any one of [1] to

[11] .

[0038] 〔13〕

[0039] A thermally conductive multilayer sheet comprising: the thermally conductive sheet described in

[12] ; and an adhesive layer or a pressure-sensitive adhesive layer provided on one or both sides of the thermally conductive sheet.

[0040]

[14]

[0041] A device with a heat-conducting layer comprises: a device; and a heat-conducting layer disposed on the device and comprising the heat-conducting sheet described in

[12] or the heat-conducting multilayer sheet described in

[13] .

[0042] Effects of the Invention

[0043] According to the present invention, a composition capable of imparting a thermally conductive material having excellent thermal conductivity can be provided.

[0044] Furthermore, according to the present invention, a thermally conductive sheet and a device with a thermally conductive layer formed of the composition can be provided. DETAILED DESCRIPTION

[0045] Hereinafter, the composition, thermally conductive sheet, and device with a thermally conductive layer of the present invention will be described in detail.

[0046] Although the constituent elements described below are described based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0047] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0048] In addition, in this 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. If possible, the epoxy group may or may not have a substituent (methyl group, etc.).

[0049] 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".

[0050] In this specification, unless otherwise specified, the anhydride group may be a monovalent group or a divalent group. In addition, when the 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 can be cited. And, when the anhydride group represents a divalent group, it represents a group represented by *-CO-O-CO-* (* represents a bonding position).

[0051] In addition, in the present specification, for substituents that are not explicitly described as substituted or unsubstituted, if possible, the group may have a substituent (for example, the substituent group Y described below) within the range that does not impair the intended effect. For example, the symbol "alkyl" means a substituted or unsubstituted alkyl group within the range that does not impair the intended effect.

[0052] In addition, in the present specification, expressions such as "may" and the like indicate that a condition set as "may" may or may not be satisfied. For example, "may have a substituent" also includes "may not have a substituent".

[0053] 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. The number of substituents can be, for example, 1 or 2 or more. As examples of substituents, monovalent non-metallic atomic groups other than hydrogen atoms can be cited, for example, which can be selected from the following substituent group Y.

[0054] In the present specification, examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

[0055] Substituent group Y:

[0056] Halogen atoms (-F, -Br, -Cl, -I, etc.), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate bases, carboxylic 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-dialkylcarbamoyloxy groups , N,N-diaryl-carbamoyloxy, N-alkyl-N-arylcarbamoyloxy, alkylthiooxy, arylthiooxy, acylthio, acylamino, N-alkylacylamino, N-arylacylamino, urea, N'-alkylurea, N',N'-dialkylurea, N'-arylurea, N',N'-diaryl-urea, 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-alkylureido, N'-aryl-N-arylureido, N',N'-diaryl--N-alkylureido, N',N'-diaryl--N-arylureido, N'-alkyl-N'-aryl-N-alkylureido, N'-alkyl-N'-aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, formyl, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N,N- Dialkylcarbamoyl, N-arylcarbamoyl, N,N-diaryl-carbamoyl, 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-diaryl-sulfamoyl, N-alkyl-N-arylsulfamoyl, sulfamoyl, N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N,N-diaryl-sulfamoyl, N-alkyl-N-arylsulfamoyl, N-acylsulfamoyl and its conjugated base, N-alkylsulfonylsulfamoyl (-SO2NHSO2(alkyl)) and its conjugated base, N-arylsulfonylsulfamoyl (-SO2NHSO2(aryl)) and its conjugated base, N-alkylsulfonylcarbamoyl (-CONHSO2(alkyl)) and its conjugated base, N-arylsulfonylcarbamoyl (-CONHSO2(aryl)) and its conjugated base, alkoxysilyl (-Si(Oalkyl)3) , allyloxysilyl (-Si(Oaryl)3), hydroxysilyl (-Si(OH)3) and its conjugate base, phosphonyl (-PO3H2) and its conjugate base, dialkylphosphonyl (-PO3(alkyl)2), diarylphosphonyl (-PO3(aryl)2), alkylarylphosphonyl (-PO3(alkyl)(aryl)), monoalkylphosphonyl (-PO3H(alkyl)) and its conjugate base, monoarylphosphonyl (-PO3H(aryl)) and its conjugate base, phosphonoxy (phosphonooxy group)(-OPO3H2) and its conjugated base, dialkylphosphonooxy group)(-OPO3(alkyl)2), diarylphosphonooxy group)(-OPO3(aryl)2), alkylarylphosphonooxy group)(-OPO3(alkyl)(aryl)), monoalkylphosphonooxy group)(-OPO3H(alkyl)) and its conjugated base, monoarylphosphonooxy group)(-OPO3H(aryl)) and its conjugated base, cyano, nitro, aryl, alkenyl, alkynyl and alkyl.

[0057] Furthermore, if possible, the substituents may or may not be bonded to each other or to the substituted group to form a ring.

[0058] [Composition]

[0059] The composition of the present invention contains an inorganic nitride and a compound represented by the general formula (1) described later (hereinafter also referred to as a specific compound).

[0060] Although the mechanism by which the composition of the present invention solves the problems of the present invention by the above-mentioned structure is not yet clear, the present inventors presume as follows.

[0061] That is, the specific compound has a structure in which a triazine ring group is bonded to three aromatic ring groups via a single bond or a specific linking group. This specific compound has high planarity and can interact strongly with an inorganic nitride and adsorb on the surface of the inorganic nitride. Therefore, the specific compound is appropriately used as a surface modifier for inorganic nitride to modify the surface of the inorganic nitride, which is used to improve the dispersibility of the inorganic nitride and improve thermal conductivity. Moreover, the specific compound has at least 2 specified groups (specific functional groups). The specific functional group causes the specific compounds to interact with each other, the specific compound and the inorganic nitride, the specific compound and other components added as desired (for example, phenolic compounds and / or epoxy compounds), etc. The inventors of the present invention speculate that since a heat conduction path is formed between inorganic nitrides through the interaction of such specific functional groups, the thermal conductivity of the thermally conductive material formed using the composition of the present invention is improved.

[0062] Furthermore, the thermally conductive sheet formed using the composition of the present invention has a smooth surface shape. The present inventors speculate that the reason for this is that the specific compound interacts well with the inorganic nitride, thereby improving the dispersibility of the inorganic nitride in the composition.

[0063] Hereinafter, the components contained in the composition will be described in detail.

[0064] 〔Inorganic nitride〕

[0065] The composition of the present invention comprises an inorganic nitride.

[0066] Examples of inorganic nitrides include 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 or 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, WN2 or WN), yttrium nitride (YN) and zirconium nitride (ZrN).

[0067] The above-mentioned inorganic nitrides may be used alone or in combination of two or more.

[0068] From the viewpoint that the thermal conductivity of the obtained surface-modified inorganic nitride is more excellent, the inorganic nitride preferably contains at least one selected from the group consisting of a boron atom, an aluminum atom, and a silicon atom. More specifically, the inorganic nitride is preferably boron nitride, aluminum nitride, or silicon nitride, more preferably boron nitride or aluminum nitride, and even more preferably boron nitride.

[0069] The shape of the inorganic nitride is not particularly limited, and examples thereof include particle, film, plate, etc. When the inorganic nitride is in particle form, examples of the particle shape include rice grain, sphere, cube, spindle, scale, aggregate, and irregular shapes.

[0070] The size of the inorganic nitride is not particularly limited. From the viewpoint of better dispersibility of the surface-modified inorganic nitride, the average particle size of the inorganic nitride 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. From the viewpoint of operability, it is preferably 10 nm or more, and more preferably 100 nm or more.

[0071] As a method for measuring the average particle size, 100 inorganic nitrides are randomly selected using an electron microscope, and the particle size (longer diameter) of each inorganic nitride is measured to obtain the arithmetic average thereof. In the case of using a commercial product, the catalog value may be used.

[0072] In the composition of the present invention, the content of the inorganic nitride is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 85% by mass based on the total solid content of the composition.

[0073] In the present specification, the solid content of the composition refers to all components other than the solvent when the composition contains a solvent, and as long as it is a component other than the solvent, even if it is a liquid component, it is regarded as a solid component.

[0074] Furthermore, the composition of the present invention may contain an inorganic substance other than the inorganic nitride ("other inorganic substances" described below).

[0075] When the composition contains other inorganic substances, the total content of the inorganic nitride and other inorganic substances is preferably 10 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 85% by mass based on the total solid content of the composition.

[0076] Furthermore, when the composition does not contain other inorganic substances, the content of the inorganic nitride is preferably 10 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 85% by mass based on the total solid content of the composition.

[0077] That is, in the composition of the present invention, the total content of inorganic substances (a general term for "inorganic nitrides" and "other inorganic substances") is preferably 10 to 95% by mass, more preferably 50 to 90% by mass, and further preferably 70 to 85% by mass relative to the total solid content of the composition.

[0078] When the content of the inorganic substance is within the above range, the thermal conductivity of the obtained thermally conductive material is further improved, and the smoothness of the obtained thermally conductive sheet is also further improved.

[0079] Furthermore, when the composition of the present invention contains other inorganic substances, the content of the inorganic nitride is preferably 10% by mass or more, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on the total amount of the inorganic substances.

[0080] The inorganic nitride may be used alone or in combination of two or more. When two or more inorganic nitrides are used, the total content thereof is preferably within the above range.

[0081] From the viewpoint of further improving the thermal conductivity of the thermally conductive material, the composition preferably contains at least an inorganic substance (preferably an inorganic nitride, more preferably boron nitride) having an average particle size of 20 μm or more (preferably 30 μm or more).

[0082] The inorganic substance contained in the composition may be only an inorganic substance (preferably an inorganic nitride, more preferably boron nitride) having an average particle size of substantially 20 μm or more (preferably 30 μm or more). The inorganic substance being substantially only an inorganic substance having an average particle size of 20 μm or more means that the content of the inorganic substance having an average particle size of 20 μm or more is greater than 99% by mass relative to the total mass of the inorganic substance.

[0083] Furthermore, the inorganic substance may include inorganic substances having different average particle diameters, and for example, may include two inorganic substances, namely, inorganic substance X having an average particle diameter of 20 μm or more, and inorganic substance Y having an average particle diameter of less than 20 μm.

[0084] The average particle size of the inorganic substance X is preferably 20 to 300 μm, more preferably 30 to 200 μm. The average particle size of the inorganic substance Y is preferably 10 nm or more and less than 20 μm, more preferably 100 nm or more and 15 μm or less.

[0085] The inorganic substance X is preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride, and further preferably boron nitride.

[0086] The inorganic substance Y is preferably an inorganic nitride or an inorganic oxide, and more preferably boron nitride or aluminum oxide.

[0087] The inorganic substance X and the inorganic substance Y may be used alone or in combination of two or more.

[0088] Among the inorganic substances, when the average particle size of the inorganic substance X is 20 to 300 μm and the average particle size of the inorganic substance Y is 10 nm or more and less than 20 μm, the mass ratio of the content of the inorganic substance X to the content of the inorganic substance Y (content of the inorganic substance X / content of the inorganic substance Y) is preferably 40 / 60 to 99 / 1, more preferably 50 / 50 to 99 / 1, and further preferably 60 / 40 to 97 / 3.

[0089] 〔Specific compounds〕

[0090] The composition of the present invention comprises a specific compound.

[0091] The specific compound is a compound represented by the general formula (1).

[0092] [Chemical formula 1]

[0093]

[0094] In the general formula (1), E 1 ~E 3 Each independently represents a single bond, -NH- or -NR-.

[0095] R represents a substituent (preferably a linear or branched alkyl group having 1 to 5 carbon atoms). 1 ~E 3 In the case where there are a plurality of -NR-, the plurality of R's may be the same or different.

[0096] 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 believed to be because E 1 ~E 3 In the case of the above-mentioned groups, the interaction between the specific compound and the inorganic nitride is further enhanced.

[0097] In the general formula (1), B 1 ~B 3 Each independently represents an aromatic ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms.

[0098] In addition, B 1 ~B 3 Relative to E 1 ~E 3 and X 1 ~X 3 They are respectively bonded to the ring-constituting atoms of the above-mentioned aromatic ring group.

[0099] The above aromatic ring group may be a monocyclic aromatic ring group or a polycyclic aromatic ring group.

[0100] The monocyclic aromatic ring group preferably has 6 to 10 ring members.

[0101] The number of rings constituting the polycyclic aromatic ring group is preferably 2 to 4, and more preferably 2. The number of ring members constituting the polycyclic aromatic ring group is preferably 5 to 10, respectively, independently.

[0102] The above-mentioned aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

[0103] The number of heteroatoms possessed by the aromatic heterocyclic group is preferably 1 to 5. Examples of the heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon and boron atoms. Among them, nitrogen, sulfur or oxygen is preferred.

[0104] B 1 ~B 3 The substituents that the aromatic ring group may have are preferably substituents other than the substituents represented by the general formula (2) described later. 1 Directly bonded B 1 The atoms in B are adjacent to each other. 1 When the atom in 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 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.

[0105] 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.

[0106] B 1 ~B 3 The number of carbon atoms as ring-constituting atoms of the aromatic ring group represented is 6 or more (preferably 6 to 12). The number of carbon atoms as ring-constituting atoms mentioned above means the number of carbon atoms as ring-constituting atoms constituting the aromatic ring.

[0107] 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 included in the number of carbon atoms as the ring-constituting atoms. In addition, the carbon atoms shared by the aromatic ring and the non-aromatic ring in the aromatic ring group are included in the number of carbon atoms as the ring-constituting atoms.

[0108] 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.

[0109] Among them, as B 1 ~B 3 , are each independently preferably a benzene ring group or a naphthyl ring group.

[0110] In the general formula (1), l, m and n each independently represent an integer of 0 or more.

[0111] l, m and n are each independently preferably 0-5, more preferably 1-2.

[0112] In addition, when l is 0, B 1 Does not have X 1 When m is 0, B 2 Does not have X 2 .

[0113] When n is 0, B 3 Does not have X 3 .

[0114] For example, when m is 0, the specific compound is a compound represented by the following general formula.

[0115] [Chemical formula 2]

[0116]

[0117] When l is 2 or more (i.e., X 1 There are multiple (l) X 1 They may be the same or different. When m is 2 or more (ie, X 2 There are multiple (m) X 2 They may be the same or different. When n is 2 or more (ie, X 3 There are multiple (n) X 3 They may be the same or different.

[0118] In the general formula (1), X 1 ~X 3 Each independently represents a group represented by the general formula (2).

[0119] [Chemical formula 3]

[0120]

[0121] In the general formula (2), * represents 1~B 3 The bonding position of any one of them.

[0122] In the general formula (2), D 1 represents a single bond or a divalent connecting group.

[0123] Examples of the divalent linking group include -O-, -S-, -CO-, and -NR N -, -SO2-, alkylene or a group consisting of these combinations. 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.

[0124] Among them, D 1 Preferably, "a single bond" or "a group consisting of a combination selected from the group consisting of -O-, -CO- and an alkylene group" is used, and more preferably, 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 .

[0125] * A Yes and A 1 Bonding position on the opposite side, * B Yes and A 1 bonding position.

[0126] In the general formula (2), A 1 The term "cycloalkyl" refers to an aromatic ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms, or a cycloalkyl ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms.

[0127] In addition, A 1 Relative to D 1 , Y 1 and Q is bonded to an atom constituting the ring of the above aromatic ring group or the above cycloalkyl ring group.

[0128] A 1 The aromatic ring group in which the carbon atoms are 6 or more and may have a substituent and B 1 ~B3 The aromatic ring groups in which the substituent is optionally substituted and the number of carbon atoms as ring-constituting atoms is 6 or more are the same.

[0129] A 1 In the cycloalkyl ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms, the cycloalkyl ring group may be a monocyclic ring or a polycyclic ring.

[0130] The monocyclic cycloalkyl ring group preferably has 6 to 10 ring members.

[0131] 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, each independently.

[0132] 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.

[0133] The number of carbon atoms as ring-constituting atoms of the cycloalkyl ring group is 6 or more (preferably 6 to 12). The number of carbon atoms as ring-constituting atoms means the number of carbon atoms as ring-constituting atoms constituting the cycloalkyl ring.

[0134] 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 included in the number of carbon atoms as the above-mentioned ring-constituting atoms. In addition, the carbon atoms shared by the cycloalkyl ring and the ring other than the cycloalkyl ring in the cycloalkyl ring group are included as the number of carbon atoms as the above-mentioned ring-constituting atoms.

[0135] As A 1 In the cycloalkyl ring group which may have a substituent and has 6 or more carbon atoms as ring constituent atoms, examples thereof include a cyclohexane ring group, a cycloheptane ring group, a norbornane ring group and an adamantane ring group.

[0136] In the general formula (2), Q and Y 1 Each independently represents a group selected from the group consisting of aldehyde group (-CHO), boric 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 specific functional group in the group having an oxetane group.

[0137] That is, the group represented by the general formula (2) is a group having at least one specific functional group. The group represented by the general formula (2) is a "group having a specific functional group", which means that the group represented by the general formula (2) can be a group that partially contains a specific functional group, or the group represented by the general formula (2) can be the specific functional group itself.

[0138] As the monovalent group having an epoxy group as the specific functional group, for example, "-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 consisting of a combination thereof.

[0139] Among them, the monovalent group having an epoxy group is preferably "-O-alkylene-epoxy group".

[0140] In addition, as a substituent which the epoxy group may have, a linear or branched alkyl group having 1 to 6 carbon atoms is preferred.

[0141] The amino group as the specific functional group is not particularly limited, and may be any of primary, secondary, and tertiary amino groups. For example, -N(R 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 further preferably 1 to 3. The alkyl group may further have a substituent. )) represents an amino group.

[0142] As the monovalent group having a carboxylic anhydride group as the specific functional group, for example, a group obtained by removing an arbitrary hydrogen atom from maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride is preferred.

[0143] As for the monovalent group having an oxetanyl group as the specific functional group, for example, "-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 consisting of a combination thereof.

[0144] Among them, the monovalent group having an oxetanyl group is preferably "-O-alkylene-oxetanyl".

[0145] In addition, as a substituent which the oxetanyl group may have, a linear or branched alkyl group having 1 to 6 carbon atoms is preferred.

[0146] 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.

[0147] In other words, Q and Y 1 Each independently preferably is an aldehyde group, a boric acid group, a hydroxyl group or a monovalent group having an epoxy group.

[0148] In the general formula (2), p represents an integer of 0 or more.

[0149] Among them, p is preferably 0-5, more preferably 0-1.

[0150] 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 the specific functional group itself.

[0151] In the general formula (2), q represents an integer of 0-2.

[0152] Among them, q is preferably 0-1.

[0153] When a plurality of groups represented by the general formula (2) are present in the specific compound, the plurality of groups represented by the general formula (2) may be the same or different.

[0154] For example, in the general formula (2), D 1 If there are multiple D 1 They can be the same or different. 1 If there are multiple A 1 They may be the same or different. When there are multiple Qs, the multiple Qs may be the same or different. 1 If there are multiple Y 1 When there are multiple ps, the multiple ps may be the same or different. When there are multiple qs, the multiple qs may be the same or different.

[0155] In the general formula (1), the total number of l, m and n is 2 or more (preferably 2 to 10, more preferably 3 to 6).

[0156] In other words, there can be multiple X 1 ~X 3 The total number is 2 or more (preferably 2 to 10, more preferably 3 to 6).

[0157] That is, in the general formula (1), there may be a plurality of X 1 The number of Xs can exist in multiple 2 The number of X and the existence of multiple 3 The total number of is 2 or more, preferably 2-10, more preferably 3-6.

[0158] For example, l is preferably 1 or more (more preferably 1 to 2), m is preferably 1 or more (more preferably 1 to 2), and n is preferably 1 or more (more preferably 1 to 2).

[0159] That is, B 1 Preferably, there are 1 or more (more preferably 1 to 2) X 1 , B 2 It is preferred to have one or more (preferably 1 to 2) X 2 , B 3 It is preferred to have one or more (preferably 1 to 2) X 3 .

[0160] Wherein, l is 1 or more, and at least one X 1 In the case of a hydroxyl group, X as the hydroxyl group 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.

[0161] m is 1 or more, and at least one X 2 In the case of a hydroxyl group, X as the hydroxyl group 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.

[0162] n is 1 or more, and at least one X 3 In the case of a hydroxyl group, X as the hydroxyl group 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.

[0163] For example, 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, the above hydroxyl group does not correspond to X 1 , and is not included in the above "there can be multiple X 1 The number of ".

[0164] The inventors of the present invention believe that the presence of 1 ~B 3 On and E 1 ~E 3The hydroxyl groups at adjacent positions are greatly affected by steric hindrance and cannot form a good thermal conduction path between the inorganic nitrides. Furthermore, the effect of improving the thermal conductivity of the thermally conductive material formed using the composition of the present invention is not sufficient.

[0165] For example, E 1 Directly bonded B 1 The atoms in the B 1 The atoms (preferably carbon atoms) in E are preferably unsubstituted. 2 Directly bonded B 2 The atoms in the B 2 The atoms (preferably carbon atoms) in E are preferably unsubstituted. 3 Directly bonded B 3 The atoms in the B 3 The atoms (preferably carbon atoms) in are preferably unsubstituted.

[0166] The specific compound may have one type or two or more types of the group represented by the general formula (2).

[0167] Among them, the specific compound is "a compound having only a hydroxyl group as a specific functional group," "a compound containing only a monovalent group having an epoxy group as a specific functional group," or "a compound having, as a specific functional group, 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".

[0168] In addition, as the above-mentioned "compound having, as specific functional groups, a group other than an aldehyde group and a boronic acid group and both an aldehyde group and / or a boronic acid group," the following compounds are preferred. For example, in the specific compound, there is one X 1 , there are m X 2 And there are n X 3 In the group (that is, among the groups represented by the general formula (2) present in 1+m+n numbers), a total of one or more groups are groups having at least one of an aldehyde group and a boronic acid group, and,

[0169] There exist l X 1 , there are m X 2 And there are n X 3 A compound in which a total of one or more (preferably 1 to 4) of the groups represented by the general formula (2) (i.e., among the groups represented by the general formula (2) that exist in 1+m+n numbers) are groups having a specific functional group other than an aldehyde group and a boronic acid group.

[0170] The above-mentioned “group having at least one 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” are preferably present as separate groups.

[0171] As the above-mentioned “specific functional group which is not an aldehyde group or a boronic acid group”, a hydroxyl group or a monovalent group having an epoxy group is preferred, and a hydroxyl group is more preferred.

[0172] The above-mentioned “group having at least one of an aldehyde group and a boronic acid group” preferably does not have a “specific functional group which is not either an aldehyde group or a boronic acid group”.

[0173] Furthermore, the above-mentioned “group having a specific functional group which is neither an aldehyde group nor a boronic acid group” preferably does not have either an aldehyde group nor a boronic acid group.

[0174] By satisfying such conditions, the thermal conductivity of the obtained thermally conductive material is further improved. The present inventors speculate that the mechanism is as follows.

[0175] That is, when the specific compound has an aldehyde group and / or a boronic acid group as the specific functional group, the aldehyde group and / or the boronic acid group interacts particularly well with an inorganic nitride (particularly boron nitride).

[0176] When the specific compound 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 nitride, and a heat conduction path based on the interaction is also formed between the above-mentioned other specific functional groups and the compound other than the inorganic nitride (for example, between the specific compounds), and the thermal conductivity of the obtained thermally conductive material is further excellent. In addition, when the composition contains the phenol compound and / or the epoxy compound described later, the above-mentioned other specific functional groups and the resin composed of the phenol compound and / or the epoxy compound sometimes form an interaction based on chemical bonding, and it is estimated that in this case, the thermal conductivity of the obtained thermally conductive material is further excellent.

[0177] Among them, the specific compound is preferably a compound represented by the general formula (1-2) or the general formula (1-3).

[0178] [Chemical formula 4]

[0179]

[0180] [Chemical formula 5]

[0181]

[0182] In the general formula (1-2) and the general formula (1-3), E 1 ~E 3Each independently represents a single bond, -NH- or -NR-. R represents a substituent.

[0183] In the general formula (1-2) and the general formula (1-3), E 1 ~E 3 With E in the general formula (1) 1 ~E 3 same.

[0184] In the general formula (1-2), g 1 ~g 3 Each independently represents an integer of 0 or 1.

[0185] In the general formula (1-2) and the general formula (1-3), 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 (2).

[0186] Among them, Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c In the formula (2), a total of 2 or more (preferably 2 to 9, more preferably 3 to 6) groups are represented by the general formula (2).

[0187] The groups represented by the general formula (2) are as described above.

[0188] Preferred Z 1a ~Z 1c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (2), and Z 2a ~Z 2c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (2), and Z 3a ~Z 3c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (2).

[0189] Among them, Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c Each of them is independently preferably "a group selected from the group of groups represented by the general formula (2) 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 (2) including a hydrogen atom and a monovalent group having an epoxy group as the specific functional group".

[0190] In addition, Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c One or more (preferably 1 to 2) of the above are groups represented by the general formula (2) having a specific functional group of at least one of an aldehyde group and a boronic acid group, and Z 1a ~Z 1c , Z 2a ~Z 2c and Z 3a ~Z 3c One or more (preferably 1 to 4) of the groups are groups represented by the general formula (2) having a specific functional group that is neither an aldehyde group nor a boronic acid group.

[0191] Among them, Z is more preferred 1a ~Z 1c One or more (preferably 1 to 2) of the above are groups represented by the general formula (2) having a specific functional group of at least one of an aldehyde group and a boronic acid group, and Z 2a ~Z 2c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (2) having a specific functional group other than an aldehyde group and a boronic acid group, and Z 3a ~Z 3c One or more (preferably 1 to 2) of the groups are groups represented by the general formula (2) having a specific functional group that is neither an aldehyde group nor a boronic acid group.

[0192] As the above-mentioned “specific functional group which is not an aldehyde group or a boronic acid group”, a hydroxyl group or a monovalent group having an epoxy group is preferred, and a hydroxyl group is more preferred.

[0193] The above-mentioned "group represented by the general formula (2) having a specific functional group other than an aldehyde group and a boronic acid group" preferably does not have a "specific functional group other than an aldehyde group and a boronic acid group".

[0194] Furthermore, the above-mentioned “group represented by the general formula (2) having a specific functional group which is neither an aldehyde group nor a boronic acid group” preferably has neither an aldehyde group nor a boronic acid group.

[0195] From the viewpoint of excellent affinity with inorganic nitrides, the HSP value (Hansen Solubility Parameter value) of the specific compound is preferably 28 MPa. 0.5 Below, more preferably 24MPa 0.5 The lower limit of the HSP value of a specific compound is not limited, but is preferably 10 MPa, for example. 0.5 above.

[0196] The HSP value of a specific compound can be calculated by the following formula.

[0197] HSP value = (HSP d 2 +HSP p 2 +HSP h 2 ) 0.5

[0198] HSP d , HSP p , HSP h They represent the dispersion term, polar term, and hydrogen bond term of the HSP value (in MPa, respectively). 0.5 ).

[0199] HSP d , HSP p , HSP h It was determined using HSPiP (Hansen Solubility Parameters in Practice (Ver.4.1.07)).

[0200] In the composition of the present invention, the content of the specific compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.5% by mass or more relative to the total solid content of the composition as a lower limit, and preferably 30% by mass or less, and more preferably 20% by mass or less as an upper limit.

[0201] Furthermore, when the composition of the present invention contains both the phenol compound described below and the epoxy compound described below, the content of the specific compound in the composition of the present invention is preferably 8% by mass or less, and more preferably 5% by mass or less, relative to the total solid content of the composition.

[0202] When the composition of the present invention contains both the phenol compound described below and the epoxy compound described below, the specific compound is preferably "a compound having both an aldehyde group and a boronic acid group and an aldehyde group and / or a boronic acid group as specific functional groups".

[0203] Furthermore, similarly, when the composition of the present invention contains only the phenolic compound described later and the phenolic compound described later (that is, when it does not substantially contain the epoxy compound described later), in the composition of the present invention, the content of the specific compound relative to the total solid content of the composition is preferably 5% by mass or more, and more preferably 12% by mass or more as the lower limit.

[0204] When the composition of the present invention contains only the phenol compound described later and the phenol compound described later (that is, when it does not substantially contain the epoxy compound described later), the specific compound is preferably a "compound having only a monovalent group having an epoxy group as a specific functional group".

[0205] In the present specification, the term "the composition contains substantially no epoxy compound" means that the content of the epoxy compound is less than 1.0% by mass (preferably 0 to 0.5% by mass, more preferably 0 to 0.1% by mass) based on the total solid content of the composition.

[0206] And, similarly, when the composition of the present invention only contains the phenol compound described later and the epoxy compound described later, the epoxy compound (that is, when the phenol compound described later is not substantially contained), the content of the specific compound in the composition of the present invention is preferably 5% by mass or more, more preferably 6% by mass or more, as a lower limit relative to the total solid content of the composition. As an upper limit, it is preferably 15% by mass or less.

[0207] When the composition of the present invention contains only the phenol compound described later and the epoxy compound described later (that is, when it does not substantially contain the phenol compound described later), the specific compound is preferably a "compound having only a hydroxyl group as a specific functional group".

[0208] In the present specification, the phrase "the composition contains substantially no phenol compound" means that the content of the phenol compound is less than 1.0% by mass (preferably 0 to 0.5% by mass, more preferably 0 to 0.1% by mass) based on the total solid content of the composition.

[0209] Furthermore, in the composition of the present invention, the content of the specific compound is preferably 0.01 to 30% by mass, more preferably 0.05 to 28% by mass, and further preferably 0.5 to 25% by mass, based on the mass of the inorganic nitride.

[0210] The specific compound may be used alone or in combination of two or more.

[0211] 〔Phenolic compounds〕

[0212] The composition of the present invention may also contain a phenolic compound.

[0213] In addition, the phenol compound is a compound other than the specific compound. For example, when the specific compound has a phenolic hydroxyl group, the specific compound does not correspond to the phenol compound.

[0214] From the viewpoint of further improving the thermal conductivity of the obtained thermally conductive material, the phenol compound is preferably at least one selected from the group consisting of compounds represented by the general formula (P1) or compounds represented by the general formula (P2).

[0215] <Compound represented by general formula (P1)>

[0216] The general formula (P1) is shown below.

[0217] [Chemical formula 6]

[0218]

[0219] In the general formula (P1), m1 represents an integer of 0 or more.

[0220] m1 is preferably 0 to 10, more preferably 0 to 3, further preferably 0 or 1, and particularly preferably 1.

[0221] In the general formula (P1), na and nc each independently represent an integer of 1 or more.

[0222] Preferably, na and nc are each independently 1 to 4.

[0223] In the general formula (P1), R 1 and R 6 Each independently represents a hydrogen atom, a halogen atom, a carboxylic acid group, a boric acid group, an aldehyde group, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

[0224] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may or may not have a substituent.

[0225] The alkyl moiety in the above-mentioned alkoxy group and the alkyl moiety in the above-mentioned alkoxycarbonyl group are the same as the above-mentioned alkyl group.

[0226] R 1 and R 6 A hydrogen atom or a halogen atom is preferred, independently of each other, a hydrogen atom or a chlorine atom is more preferred, and a hydrogen atom is further preferred.

[0227] In the general formula (P1), R 7 represents a hydrogen atom or a hydroxyl group.

[0228] R 7 If there are multiple R 7 They may be the same or different.

[0229] R 7 When there are multiple R 7 At least one R 7 Represents hydroxyl.

[0230] In the general formula (P1), L x1 represents a single bond, -C(R 2 )(R 3 )- or -CO-, preferably -C(R2 )(R 3 )-or-CO-.

[0231] L x2 represents a single bond, -C(R 4 )(R 5 )- or -CO-, preferably -C(R 4 )(R 5 )-or-CO-.

[0232] R 2 ~R 5 Each independently represents a hydrogen atom or a substituent.

[0233] The above substituents are each independently preferably a hydroxyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, and more preferably a hydroxyl group, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

[0234] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may or may not have a substituent.

[0235] The alkyl moiety in the above-mentioned alkoxy group and the alkyl moiety in the above-mentioned alkoxycarbonyl group are the same as the above-mentioned alkyl group.

[0236] The phenyl group may or may not have a substituent, and when having a substituent, it is more preferable that the phenyl group has 1 to 3 hydroxyl groups.

[0237] R 2 ~R 5 A hydrogen atom or a hydroxyl group is respectively independently preferred, and a hydrogen atom is more preferred.

[0238] L x1 and L x2 Each of them independently is preferably -CH2-, -CH(OH)-, -CO- or -CH(Ph)-.

[0239] The above-mentioned Ph represents a phenyl group which may have a substituent.

[0240] In the general formula (P1), R 4 If there are multiple R 4 They may be the same or different. 5 If there are multiple R 5 They may be the same or different.

[0241] In the general formula (P1), Ar 1 and Ar 2 Each independently represents a benzene ring group or a naphthyl ring group.

[0242] Ar 1 and Ar 2 Each independently a benzene ring group is preferred.

[0243] In the general formula (P1), Q a represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boric acid group, an aldehyde group, an alkoxy group or an alkoxycarbonyl group.

[0244] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may or may not have a substituent.

[0245] The alkyl moiety in the above-mentioned alkoxy group and the alkyl moiety in the above-mentioned alkoxycarbonyl group are the same as the above-mentioned alkyl group.

[0246] The above-mentioned phenyl group may or may not have a substituent.

[0247] Q a Relative to Q a The hydroxyl group which the benzene ring group to be bonded may have is preferably bonded at the para position.

[0248] Q a A hydrogen atom or an alkyl group is preferred. The alkyl group is preferably a methyl group.

[0249] In the general formula (P1), R 7 , L x2 and / or Q a If there are multiple R 7 , L x2 and / or Q a They may be the same or different.

[0250] (Compound represented by general formula (P2))

[0251] The general formula (P2) is shown below

[0252] [Chemical formula 7]

[0253]

[0254] In the general formula (P2), m2 represents an integer of 0 or more.

[0255] m2 is preferably 0-10, more preferably 0-4.

[0256] In the general formula (P2), nx represents an integer of 0-4.

[0257] nx is preferably 1-2, more preferably 2.

[0258] In the general formula (P2), ny represents an integer of 0-2.

[0259] When there are a plurality of ny, the plurality of ny may be the same as or different from each other.

[0260] At least one ny among the ny that may exist in plurality preferably represents 1. For example, when m2 represents 1, one ny that exists preferably represents 1. When m2 represents 4, at least one ny among the 4 ny that exist preferably represents 1, and more preferably two ny that exist represent 1.

[0261] In the general formula (P2), nz represents an integer of 0-2.

[0262] nz preferred 1.

[0263] In the general formula (P2), the total number of nx, ny (which may exist in plural numbers), and nz is preferably 2 or more, more preferably 2-10.

[0264] In the general formula (P2), R 1 and R 6 Each independently represents a hydrogen atom, a halogen atom, a carboxylic acid group, a boric acid group, an aldehyde group, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

[0265] R in the general formula (P2) 1 and R 6 With R in the general formula (P1) 1 and R 6 Respectively the same.

[0266] R 1 If there are multiple R 1 They may be the same or different. 6 If there are multiple R 6 They may be the same or different.

[0267] In the general formula (P2), Q b represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boric acid group, an aldehyde group, an alkoxy group or an alkoxycarbonyl group.

[0268] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group may or may not have a substituent.

[0269] The alkyl moiety in the above-mentioned alkoxy group and the alkyl moiety in the above-mentioned alkoxycarbonyl group are the same as the above-mentioned alkyl group.

[0270] The above-mentioned phenyl group may or may not have a substituent.

[0271] Q b A hydrogen atom is preferred.

[0272] Q b When there are multiple Q bThey may be the same or different.

[0273] Specific examples of the compound represented by the general formula (P2) include benzenetriol (preferably 1,3,5-benzenetriol).

[0274] As other phenol compounds, for example, preferred are biphenyl aralkyl type phenolic resins, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenolic resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins, polyphenol novolac resins synthesized from polyhydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylethane resins, naphthol novolac resins, naphthol phenolic varnish resins, naphthol phenol co-condensation novolac resins, naphthol cresol co-condensation novolac resins, biphenyl modified phenolic resins, biphenyl modified naphthol resins, aminotriazine modified phenolic resins and alkoxy-containing aromatic ring modified novolac resins.

[0275] The lower limit of the hydroxyl content of the phenol compound is preferably 3.0 mmol / g or more, more preferably 8.0 mmol / g or more, further preferably 11.0 mmol / g or more, particularly preferably 12.0 mmol / g or more, and most preferably 13.0 mmol / g or more. The upper limit is preferably 25.0 mmol / g or less, more preferably 23.0 mmol / g or less.

[0276] The above-mentioned hydroxyl group content refers to the number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in 1 g of the phenol compound.

[0277] Furthermore, the phenol compound may or may not have an active hydrogen-containing group (carboxylic acid group, etc.) capable of polymerizing with the epoxy compound in addition to the hydroxyl group. The lower limit of the active hydrogen content of the phenol compound (the total content of hydrogen atoms in the hydroxyl group and the carboxylic acid group, etc.) is preferably 8.0 mmol / g or more, more preferably 10.5 mmol / g or more, further preferably 11.0 mmol / g or more, particularly preferably 12.0 mmol / g or more, and most preferably 13.0 mmol / g or more. The upper limit is preferably 25.0 mmol / g or less, more preferably 23.0 mmol / g or less.

[0278] The upper limit of the molecular weight of the phenol compound is preferably 600 or less, more preferably 500 or less, further preferably 450 or less, particularly preferably 400 or less. The lower limit is preferably 110 or more, more preferably 300 or more.

[0279] The phenol compound may be used alone or in combination of two or more.

[0280] When the composition of the present invention contains a phenol compound, the content of the phenol compound is preferably 1.0 to 25.0% by mass, more preferably 3.0 to 20.0% by mass, based on the total solid content of the composition.

[0281] Furthermore, the composition of the present invention may contain, as a compound other than the phenol compound and the specific compound, a compound having a group reactive with an epoxy compound described later (also referred to as “other active hydrogen-containing compound”).

[0282] When the composition of the present invention contains a phenol compound and other active hydrogen-containing compounds, the mass ratio of the content of the other active hydrogen-containing compound to the content of the phenol compound in the composition of the present invention (content of other active hydrogen-containing compounds / content of phenol compounds) is preferably 0 to 1, more preferably 0 to 0.1, and even more preferably 0 to 0.05.

[0283] 〔Epoxides〕

[0284] The composition of the present invention may further comprise an epoxy compound.

[0285] In addition, the epoxy compound is a compound other than the specific compound. For example, when the specific compound has an epoxy group, the specific compound does not correspond to the epoxy compound.

[0286] 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.

[0287] The number of epoxy groups contained in the epoxy compound is preferably 2 or more, more preferably 2 to 40, further preferably 2 to 10, and particularly preferably 2 in one molecule.

[0288] 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.

[0289] 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, and more preferably 15.0 mmol / g or less.

[0290] In addition, the said epoxy group content means the number of epoxy groups which 1g of an epoxy compound has.

[0291] The epoxy compound is preferably in a liquid state at room temperature (23°C).

[0292] Epoxy compounds may or may not exhibit liquid crystallinity.

[0293] That is, the epoxy compound may be a liquid crystal compound. In other words, a liquid crystal compound having an epoxy group can also be used as the epoxy compound.

[0294] Examples of the epoxy compound (which may be a liquid crystalline epoxy compound) include a compound including at least partially a rod-like structure (rod-like compound) and a compound including at least partially a disc-like structure (disc-like compound).

[0295] Among them, rod-shaped compounds are preferred because the thermal conductivity of the obtained thermally conductive material is more excellent.

[0296] Hereinafter, the rod-shaped compound and the disc-shaped compound will be described in detail.

[0297] (Rod-like compound)

[0298] Examples of the epoxy compound of the rod-shaped compound include azomethine, azoxy, cyanobiphenyl, cyanophenyl ester, benzoate, cyclohexanecarboxylic acid phenyl ester, cyanophenylcyclohexane, cyano-substituted phenylpyrimidine, alkoxy-substituted phenylpyrimidine, phenyldioxane, tolan and alkenylcyclohexylbenzonitrile. Not only the above low molecular weight compounds 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.

[0299] Preferred examples of the rod-shaped compound include rod-shaped compounds represented by the following general formula (XXI).

[0300] General formula (XXI): Q 1 -L 111 -A 111 -L 113 -ML 114 -A 112 -L 112 -Q 2

[0301] In the general formula (XXI), Q 1 and Q 2 are independently epoxy groups, L 111 , L 112 , L 113 and L 114 Each independently represents a single bond or a divalent linking group. 111 and A 112 Each independently represents a divalent linking group (spacer) having 1 to 20 carbon atoms. M represents a mesogenic group.

[0302] Q 1 and Q 2 The epoxy group may or may not have a substituent.

[0303] In the general formula (XXI), L 111 , L 112 , L 113 and L 114 Each independently represents a single bond or a divalent linking group.

[0304] As L 111 , L 112 , L 113 and L 114 The divalent linking groups represented by are preferably independently selected from -O-, -S-, -CO-, -NR 112 -, -CO-O-, -O-CO-O-, -CO-NR 112 -、-NR 112 -CO-, -O-CO-, -CH2-O-, -O-CH2-, -O-CO-NR 112 -、-NR 112 -CO-O- and -NR 112 -CO-NR 112 -a divalent connecting group in the group. 112 It is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.

[0305] Among them, L 113 and L 114 Each independently is preferably -O-.

[0306] L 111 and L 112 Each independently a single bond is preferred.

[0307] In the general formula (XXI), A 111 and A 112 Each independently represents a divalent linking group having 1 to 20 carbon atoms.

[0308] The divalent linking group may contain non-adjacent heteroatoms such as oxygen atoms and sulfur atoms. Among them, an alkylene group, an alkenylene group or an alkynylene group having 1 to 12 carbon atoms is preferred. The above-mentioned alkylene group, alkenylene group or alkynylene group may or may not have an ester group.

[0309] The divalent linking group is preferably linear, and may or may not have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, and bromine atom), a cyano group, a methyl group, and an ethyl group.

[0310] Among them, A 111 and A 112 Each independently is preferably an alkylene group having 1 to 12 carbon atoms, and more preferably a methylene group.

[0311] In the general formula (XXI), M represents a mesogenic group, and examples of the mesogenic group include known mesogenic groups. Among them, groups represented by the following general formula (XXII) are preferred.

[0312] General formula (XXII): -(W 1 -L 115 ) n -W 2 -

[0313] In the general formula (XXII), W 1 and W 2 Each independently represents a divalent cyclic alkylene group, a divalent cyclic alkenylene group, an arylene group or a divalent heterocyclic group. 115 represents a single bond or a divalent linking group. n represents an integer of 1 to 4.

[0314] As W 1 and W 2 For example, 1,4-cyclohexadienyl, 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl and pyridazine-3,6-diyl 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, and a mixture of any ratio may be used. Among them, the trans-isomer is preferred.

[0315] W 1 and W 2 Each of the alkyl groups may have a substituent. As the substituent, for example, the groups exemplified in the above substituent group Y can be cited, and more specifically, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, alkyl groups having 1 to 10 carbon atoms (for example, methyl groups, ethyl groups, and propyl groups), alkoxy groups having 1 to 10 carbon atoms (for example, methoxy groups and ethoxy groups), acyl groups having 1 to 10 carbon atoms (for example, formyl groups and acetyl groups), alkoxycarbonyl groups having 1 to 10 carbon atoms (for example, methoxycarbonyl groups and ethoxycarbonyl groups), acyloxy groups having 1 to 10 carbon atoms (for example, acetoxy groups and propionyloxy groups), nitro groups, trifluoromethyl groups, and difluoromethyl groups can be cited.

[0316] W 1 If there are multiple W 1 They may be the same or different.

[0317] In the general formula (XXII), L 115 represents a single bond or a divalent linking group. 115 The divalent linking group represented by may be the above-mentioned L 111~L 114 Specific examples of the divalent linking group represented by include -CO-O-, -O-CO-, -CH2-O-, and -O-CH2-.

[0318] L 115 If there are multiple L 115 They may be the same or different.

[0319] Preferred basic skeletons of the mesogenic group represented by the general formula (XXII) are shown below. The mesogenic group may have a substituent substituted on the skeleton.

[0320] [Chemical formula 8]

[0321]

[0322] [Chemical formula 9]

[0323]

[0324] Among the above skeletons, a biphenyl skeleton is preferred from the viewpoint that the thermal conductivity of the obtained thermally conductive sheet is more excellent.

[0325] The compound represented by the general formula (XXI) can be synthesized by referring to the method described in JP-A-11-513019 (WO97 / 00600).

[0326] The rod-shaped compound may be a monomer having a mesogenic group as described in Japanese Patent Application Laid-Open No. 11-323162 and Japanese Patent No. 4118691.

[0327] Among them, the rod-shaped compound is preferably a compound represented by the general formula (E1).

[0328] [Chemical formula 10]

[0329]

[0330] In the general formula (E1), L E1 Each independently represents a single bond or a divalent linking group.

[0331] Among them, L E1 A divalent linking group is preferred.

[0332] The divalent linking group is preferably -O-, -S-, -CO-, -NH-, -CH=CH-, -C≡C-, -CH=N-, -N=CH-, -N=N-, an alkylene group which may have a substituent, or a group consisting of two or more of these groups in combination, and -O-alkylene- or -alkylene-O- is more preferred.

[0333] The alkylene group may be linear, branched or cyclic, and is preferably a linear alkylene group having 1 to 2 carbon atoms.

[0334] There are multiple L E1 They may be the same or different.

[0335] 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-.

[0336] Among them, L E2 A single bond, -CO-O- or -O-CO- is respectively preferred independently.

[0337] L E2 If there are multiple L E2 They may be the same or different.

[0338] In the general formula (E1), L E3 Each independently represents a single bond or an optionally substituted 5- or 6-membered aromatic ring group, a 5- or 6-membered non-aromatic ring group, or a polycyclic group consisting of these rings.

[0339] As L E3 Examples of the aromatic ring group and the non-aromatic ring group represented by the present invention include 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 which may have a substituent. In the case of 1,4-cyclohexanediyl, any isomer of the structural isomers of the trans-isomer and the cis-isomer may be used, and a mixture of any ratio may be used. Among them, the trans-isomer is preferred.

[0340] Among them, L E3 A single bond, 1,4-phenylene or 1,4-cyclohexadienyl is preferred.

[0341] L E3 The substituents possessed by the groups represented 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).

[0342] When there are plural substituents, the substituents may be the same or different.

[0343] L E3 If there are multiple L E3 They may be the same or different.

[0344] In the general formula (E1), pe represents an integer of 0 or more.

[0345] When pe is an integer greater than 2, there are multiple (-L E3 -L E2 -) can be the same or different.

[0346] Among them, pe is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0347] In the general formula (E1), L E4 Each independently represents a substituent.

[0348] 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).

[0349] There are multiple L E4 They may be the same or different. Furthermore, when le described below is an integer greater than 2, in the same (L E4 ) le There are multiple L E4 They may be the same or different.

[0350] In the general formula (E1), le each independently represents an integer of 0-4.

[0351] Among them, le is preferably 0 to 2 each independently.

[0352] A plurality of le's may be the same or different.

[0353] The rod-shaped compound preferably has a biphenyl skeleton.

[0354] In other words, the epoxy compound preferably has a biphenyl skeleton, and the epoxy compound in this case is more preferably a rod-shaped compound.

[0355] (Disc-shaped compound)

[0356] The epoxy compound which is a disc-shaped compound has a disc-shaped structure at least partially.

[0357] 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.

[0358] Specific examples of the disc-shaped structure include triphenylene structures described in Angew. Chem. Int. Ed. 2012, 51, 7990-7993 or JP-A-7-306317 and tri-substituted benzene structures described in JP-A-2007-002220 and JP-A-2010-244038.

[0359] 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.

[0360] The number of epoxy groups contained in the disc-shaped compound is preferably 8 or less, more preferably 6 or less.

[0361] Specific 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 of the terminals (preferably 3 or more) is an epoxy group.

[0362] Examples of the disc-shaped compound include the triphenylene structure described in Angew. Chem. Int. Ed. 2012, 51, 7990-7993 and Japanese Patent Application Publication No. 7-306317, and the tri-substituted benzene structure described in Japanese Patent Application Publication No. 2007-002220 and Japanese Patent Application Publication No. 2010-244038, in which at least one (preferably 3 or more) terminal is an epoxy group.

[0363] (Other Epoxides)

[0364] As other epoxy compounds other than the above-mentioned epoxy compounds, epoxy compounds represented by General Formula (DN) are mentioned, for example.

[0365] [Chemical formula 11]

[0366]

[0367] 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.

[0368] 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 consisting of a combination thereof, more preferably an alkylene group, and more preferably a methylene group.

[0369] As other epoxy compounds, there can be mentioned compounds in which epoxy groups are ring-condensed.

[0370] Examples of such a compound include 3,4:8,9-diepoxybicyclo[4.3.0]nonane.

[0371] As other epoxy compounds, for example, bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, bisphenol AD ​​epoxy compounds, etc., which are glycidyl ethers of bisphenol A, F, S, AD, etc.; hydrogenated bisphenol A epoxy compounds, hydrogenated bisphenol AD ​​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 ether, etc.; dicyclopentadiene type glycidyl ether (dicyclopentadiene type epoxy compound); dihydroxypentadiene type glycidyl ether (dihydroxypentadiene type epoxy compound); polyhydroxybenzene type glycidyl ether (polyhydroxybenzene type epoxy compound); benzene polycarboxylic acid type glycidyl ester (benzene polycarboxylic acid type epoxy compound); and trisphenol methane type epoxy compound.

[0372] The epoxy compounds may be used alone or in combination of two or more.

[0373] 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, based on the total solid content of the composition.

[0374] The composition of the present invention preferably contains at least one of the above-mentioned phenol compound and epoxy compound.

[0375] In this case, as described above, the composition may contain only the phenol compound (which may not contain substantially the epoxy compound) of the phenol compound and the epoxy compound, may contain only the epoxy compound (which may not contain substantially the phenol compound), or may contain both of them.

[0376] When the composition of the present invention contains an epoxy compound and a phenol compound respectively, the ratio of the content of the epoxy compound to the content of the phenol compound in the composition, the equivalent ratio of the epoxy group of the epoxy compound to the hydroxyl group of the phenol compound (the number of epoxy groups / the number of hydroxyl groups) is preferably 30 / 70 to 70 / 30, and more preferably 35 / 65 to 65 / 35.

[0377] Furthermore, when the composition of the present invention contains an epoxy compound and a phenol compound, respectively, the ratio of the content of the epoxy compound to the content of the phenol compound in the composition, the equivalent ratio (number of epoxy groups / number of active hydrogen) of the epoxy group of the epoxy compound to the active hydrogen (hydrogen atoms in the hydroxyl group, etc.) of the phenol compound is preferably 30 / 70 to 70 / 30, and more preferably 35 / 65 to 65 / 35.

[0378] Furthermore, the ratio of the number of epoxy groups, which is the sum of the number of epoxy groups contained in the epoxy compound and the number of epoxy groups contained in the specific compound, to the number of hydroxyl groups, which is the sum of the number of hydroxyl groups contained in the phenol compound and the number of hydroxyl groups contained in the specific compound in the composition (the number of epoxy groups / the number of hydroxyl groups) is preferably 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and further preferably 42 / 58 to 58 / 42.

[0379] In this case, the composition may contain only one of the epoxy compound and the phenol compound, may contain both, or may not contain both.

[0380] Furthermore, when the composition contains the specific compound having an epoxy group, the specific compound having active hydrogen and / or a compound containing other active hydrogen, with respect to the ratio of the total content of the epoxy compound and the specific compound having an epoxy group to the total content of the phenol compound, the specific compound having active hydrogen and the compound containing other active hydrogen, the equivalent ratio (number of epoxy groups / number of active hydrogen) of the epoxy group to the active hydrogen (hydrogen atoms in the hydroxyl group, etc.) in the system is preferably 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and even more preferably 42 / 58 to 58 / 42.

[0381] When the composition of the present invention contains both an epoxy compound and a phenol compound, the total content of the phenol compound and the epoxy compound is preferably 5 to 90% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass based on the total mass of the solid content in the composition.

[0382] 〔Other inorganic substances〕

[0383] The composition of the present invention may contain other inorganic substances as inorganic substances other than the inorganic nitride.

[0384] As the other inorganic substance, inorganic oxides are preferred from the viewpoint that the thermal conductivity and insulation properties of the obtained thermally conductive material are more excellent.

[0385] 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.

[0386] The above-mentioned inorganic oxides may be used alone or in combination of two or more.

[0387] The inorganic oxide is preferably titanium oxide, aluminum oxide or zinc oxide, more preferably aluminum oxide.

[0388] The inorganic oxide may be an oxide generated by oxidation of a metal prepared as a non-oxide under an environment or the like.

[0389] The shape of other inorganic substances is not particularly limited, and may be in the form of particles, films, or plates. Examples of the shape of the particulate inorganic substances include rice grains, spheres, cubes, spindles, scales, aggregates, and irregular shapes.

[0390] The size of other inorganic substances is not particularly limited. From the perspective of better dispersibility of other inorganic substances, the average particle size of other inorganic substances 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. From the perspective of operability, it is preferably 10 nm or more, and more preferably 100 nm or more.

[0391] When commercial products are used as the average particle diameter of other inorganic substances, the product catalog value is adopted. When there is no product catalog value, as a method for measuring the above average particle diameter, 100 inorganic substances are randomly selected using an electron microscope, and the particle diameter (major diameter) of each inorganic substance is measured to obtain their arithmetic mean value.

[0392] Other inorganic substances may be used in one kind only or in two or more kinds. When two or more kinds are used, it is also preferred to use two or more kinds of other inorganic substances with different average particle sizes. For example, it is also preferred to use both other inorganic substances with an average particle size of 1 to 200 μm and other inorganic substances with an average particle size of 100 nm or more and less than 1 μm.

[0393] When the composition contains other inorganic substances, the content of the other inorganic substances in the composition is preferably 10 to 95% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 45% by mass based on the total solid content of the composition.

[0394] 〔Other surface modifiers〕

[0395] Furthermore, regarding the composition (preferably when the composition contains other inorganic substances (inorganic oxides, etc.)), it is also preferred to contain an organic silane molecule (preferably a compound having an alkoxysilyl group) as another surface modifier (preferably a surface modifier for inorganic oxides, more preferably a surface modifier for aluminum oxide) other than the specific compound.

[0396] Examples of the organic silane molecules that are the other surface modifiers include 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane and 3-ureapropyltriethoxysilane.

[0397] The surface modifier may be used alone or in combination of two or more.

[0398] The content of the organosilane molecules as a surface modifier (preferably organosilane molecules as other surface modifiers) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the content of other inorganic substances (preferably inorganic oxides such as alumina).

[0399] 〔Curing accelerator〕

[0400] The composition may also contain a curing accelerator.

[0401] The type of curing accelerator is not limited, and examples thereof include triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, 1-benzyl-2-methylimidazole, and compounds described in paragraph 0052 of JP-A-2012-067225.

[0402] The curing accelerator may be used alone or in combination of two or more.

[0403] 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 epoxy compound and the specific compound having an epoxy group.

[0404] 〔Dispersant〕

[0405] The composition may also contain a dispersant.

[0406] 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.

[0407] The dispersant can 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.), Ajisper PN-411 (manufactured by Ajinomoto Fine-Techno Co., Inc.), and REB122-4 (manufactured by Hitachi Chemical Co., Ltd.) can be cited.

[0408] The dispersants may be used alone or in combination of two or more.

[0409] 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, based on the content of the inorganic substance.

[0410] 〔Solvent〕

[0411] The composition may also contain a solvent.

[0412] The type of solvent is not particularly limited, but an organic solvent is preferred. Examples of the organic solvent include cyclopentanone, cyclohexanone, ethyl acetate, methylethylcopper, dichloromethane, and tetrahydrofuran.

[0413] When the composition contains a solvent, the content of the solvent is preferably an amount such that the solid content concentration of the composition is 20 to 90% by mass, more preferably 30 to 85% by mass, and even more preferably 40 to 85% by mass.

[0414] [Method for producing the composition]

[0415] 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 all at once or sequentially.

[0416] The method for mixing the components is not particularly limited, and known methods can be used. The mixing device used for mixing is preferably a liquid disperser, for example, a mixer such as a rotation-revolution mixer, a high-speed rotary shearing mixer, a colloid 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 during mixing.

[0417] [Method for curing the composition]

[0418] The composition of the present invention is preferably a composition for forming a thermally conductive material.

[0419] The thermally conductive material can be obtained by curing the composition of the present invention.

[0420] The curing method of the composition is not particularly limited, but thermal curing reaction is preferred.

[0421] The heating temperature during the thermal curing reaction is not particularly limited and may be appropriately selected from the range of 50 to 250° C. Furthermore, during the thermal curing reaction, the heating treatment may be performed multiple times at different temperatures.

[0422] The curing treatment is preferably performed on the composition in the form of a film or a sheet. Specifically, for example, the film-forming composition is applied and the curing reaction is performed.

[0423] 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, the curing treatment can be further performed after a different substrate is brought into contact with the coating film formed on the substrate. The cured product (thermal conductive material) obtained after curing may be separated from one or both of the substrates, or may not be separated.

[0424] Furthermore, when performing the curing treatment, the composition can be applied to each substrate to form a coating film, and the coating films obtained can be cured in a state of contacting each other. The cured product (thermal conductive material) obtained after curing can be separated from one or both of the substrates, or can be kept intact.

[0425] During the curing process, a press process may be performed. There is no limitation on the press machine used for the press process, and for example, a flat plate press machine or a roller press machine may be used.

[0426] When a roller press is used, for example, it is preferred that a substrate with a coating film formed on a substrate is clamped between a pair of rollers opposed to each other, and the pair of rollers is rotated to allow the substrate with the coating film to pass through, and pressure is applied to the film thickness direction of the substrate with the coating film. The substrate with the coating film may exist only on one side of the coating film, or may exist on both sides of the coating film. The substrate with the coating film may pass through the roller press only once, or may pass through multiple times.

[0427] Only one of the treatment by the platen press and the treatment by the roller press may be performed, or both of them may be performed.

[0428] Furthermore, the curing treatment may be terminated when the composition becomes a semi-cured state. After the semi-cured thermal conductive material of the present invention is arranged in contact with the device to be used, it may be further cured by heating or the like and fully cured. The device is preferably bonded to the thermal conductive material of the present invention by heating or the like during the above-mentioned full curing.

[0429] 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 Publishing Co., Ltd., written by Takezawa Yutaka).

[0430] The shape of the heat conductive material is not particularly limited, and can be molded into various shapes according to the application. A typical shape of the molded heat conductive material is, for example, a sheet shape.

[0431] That is, the thermally conductive material obtained using the composition of the present invention is also preferably a thermally conductive sheet.

[0432] Furthermore, the thermal conductivity of the thermally conductive material obtained using the composition of the present invention is preferably isotropic rather than anisotropic.

[0433] 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.

[0434] 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.

[0435] [Application of thermal conductive materials]

[0436] 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 purposes 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, and the heat generated by the device can be effectively dissipated through the thermally conductive layer. The thermally conductive layer may be a thermally conductive layer containing a thermally conductive multilayer sheet described later.

[0437] Since the thermally conductive material obtained by using the composition of the present invention has sufficient thermal conductivity and high heat resistance, it is suitable for heat dissipation of power semiconductor devices used in various electronic devices such as personal computers, general household appliances and automobiles.

[0438] Furthermore, since the thermally conductive material obtained by using the composition of the present invention has sufficient thermal conductivity even in a semi-cured state, it can also be used as a heat dissipation material for locations that are difficult to reach with light for photocuring, such as gaps between components of various devices. Furthermore, since it has excellent adhesion, it can also be used as a thermally conductive adhesive.

[0439] The thermally conductive material obtained by using the composition of the present invention can be used in combination with other members other than the member formed of the present composition.

[0440] 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.

[0441] As the sheet-like support, 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 silicone can be cited. As the metal film, a copper film can be cited.

[0442] 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.

[0443] Furthermore, a thermally conductive material (preferably a thermally conductive sheet) may be combined with an adhesive layer and / or a pressure-sensitive adhesive layer.

[0444] By bonding the thermally conductive material to an object that requires heat transfer, such as a device, via such an adhesive layer and / or a pressure-sensitive adhesive layer, it is possible to achieve more firmly bonding the thermally conductive material and the object.

[0445] For example, as the thermally conductive multilayer sheet, a thermally conductive multilayer sheet including a thermally conductive sheet and a pressure-sensitive adhesive layer or a sticky agent layer provided on one or both surfaces of the thermally conductive sheet may be prepared.

[0446] In addition, one or both of the adhesive layer and the adhesive layer may be provided on one or both sides of the thermal conductive sheet. An adhesive layer may be provided on one side of the thermal conductive sheet, and an adhesive layer may be provided on the other side. Furthermore, an adhesive layer and / or an adhesive layer may be provided partially on one or both sides of the thermal conductive sheet, or may be provided on the entire surface.

[0447] In addition, as described above, in the present invention, the thermally conductive material such as the thermally conductive sheet may be in a semi-cured state (semi-cured film), the thermally conductive sheet in the thermally conductive multilayer sheet may be in a semi-cured state, and the adhesive layer in the thermally conductive multilayer sheet may be cured, semi-cured, or uncured.

[0448] <Adhesive layer>

[0449] The adhesive layer preferably contains at least one compound having adhesive properties (resin and / or low molecular weight substance, etc.).

[0450] The adhesive layer may contain other components such as a filler as necessary.

[0451] As the compound having adhesive properties, a compound having insulating properties, adhesive properties and / or flexibility is preferred during bonding.

[0452] Among them, from the viewpoint of adhesiveness and insulation properties, it is preferred to contain at least one selected from the group consisting of polyimide resins, modified polyimide resins, polyamideimide resins, modified polyamideimide resins, and epoxy compounds.

[0453] The epoxy compound may be an epoxy resin containing acrylic modified rubber.

[0454] Examples of the polyimide resin and modified polyimide resin include Yupicoat FS-100L (manufactured by BE INDUSTRIES, LTD.), Semico Fine SP-300, SP-400, SP-800 (manufactured by TORAY INDUSTRIES, INC.), and U-imide series (manufactured by UNITIKA LTD.).

[0455] Examples of the polyamide-imide resin or modified polyamide-imide resin include KS series (manufactured by Hitachi Chemical Co., Ltd.), Viromax series (manufactured by TOYOBO Co., Ltd.), and Torlon (manufactured by Solvay Advanced Polymers).

[0456] Among them, KS series (manufactured by Hitachi Chemical Co., Ltd.) is preferably used from the viewpoint of high heat resistance and high adhesiveness.

[0457] Modified polyamide-imide resin represented by.

[0458] The polyimide resin, polyamide-imide resin, and modified polyamide-imide resin used in the adhesive layer may be used alone or in combination of two or more.

[0459] Furthermore, these resins are usually in a varnish state in which the resin is dissolved in a solvent, and can also be used as an adhesive layer by directly applying it on a support such as a PET film and drying the solvent to form a film.

[0460] Furthermore, as the compound having adhesiveness, an epoxy compound can be used. Specifically, for example, an epoxy composition comprising an epoxy compound, a curing agent thereof, and a curing accelerator can be used as the adhesive layer. It is also preferred to add glycidyl acrylate to the epoxy composition.

[0461] For details of the epoxy composition, reference can also be made to the descriptions of, for example, Japanese Patent Application Laid-Open Nos. 2002-134531, 2002-226796, and 2003-221573.

[0462] The epoxy compound used in the adhesive layer is not particularly limited as long as it exhibits adhesion by curing. For example, if a liquid epoxy compound of bisphenol A type or bisphenol F type with a molecular weight of less than 500 is used, the fluidity during lamination is improved. In order to achieve a high Tg (glass transition temperature), a multifunctional epoxy compound can be added. As the multifunctional epoxy compound, for example, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, etc. can be cited.

[0463] As the epoxy compound used in the adhesive layer, the epoxy compounds described as the epoxy compounds that can be used in the composition of the present invention can be used.

[0464] As the curing agent of the epoxy compound, for example, polyamide, polyamine, acid anhydride, polysulfide, boron trifluoride or phenol compound (phenol novolac resin, a compound having two or more phenolic hydroxyl groups in one molecule, i.e., bisphenol A, bisphenol F or bisphenol S, etc.) can be cited. From the viewpoint of excellent electrical corrosion resistance during moisture absorption, phenol novolac resin, bisphenol novolac resin or cresol novolac resin, etc., which are phenol compounds, are also preferably used.

[0465] Furthermore, as the curing agent, the phenol compounds described as the phenol compounds that can be used in the composition of the present invention can be used.

[0466] When a curing agent is used, it is preferred to use a curing accelerator together with the curing agent. As a curing accelerator, it is also preferred to use imidazole. As imidazole, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate can be mentioned. Imidazoles are commercially available, for example, from SHIKOKU CHEMICALS CORPORATION under the product names of 2E4MZ, 2PZ-CN, and 2PZ-CNS.

[0467] As the curing accelerator, the curing accelerators described as the effect accelerators (triphenylphosphine and the like) that can be used in the composition of the present invention can be used.

[0468] The epoxy compound used in the adhesive layer is preferably used together with a high molecular weight resin compatible with the epoxy compound.

[0469] Examples of the high molecular weight resin compatible with the epoxy compound include a high molecular weight epoxy compound, a rubber containing a highly polar functional group, and a reactive rubber containing a highly polar functional group.

[0470] Examples of the reactive rubber containing a highly polar functional group include acrylic modified rubbers obtained by adding a highly polar functional group such as a carboxyl group to an acrylic rubber.

[0471] Here, being compatible with the epoxy compound means that after curing, the epoxy compound does not separate into two or more phases but forms a homogeneous mixture.

[0472] The weight average molecular weight of the high molecular weight resin is not particularly limited, but is preferably 30,000 or more from the viewpoint of reducing the viscosity of the adhesive in the B stage or improving the flexibility during curing.

[0473] The high molecular weight epoxy compound has a molecular weight of 30,000 to 80,000, and there is an ultra-high molecular weight epoxy compound having a molecular weight greater than 80,000 (see Japanese Patent Publication No. 7-059617, Japanese Patent Publication No. 7-059618, Japanese Patent Publication No. 7-059619, Japanese Patent Publication No. 7-059620, Japanese Patent Publication No. 7-064911, Japanese Patent Publication No. 7-068327), all of which are manufactured by Hitachi Chemical Co., Ltd. As a reactive rubber containing a functional group with a large polarity, a carboxyl group-containing acrylic rubber is sold, for example, as HTR-860P (product name) by Nagase Chemtex Corporation.

[0474] When a high molecular weight resin having compatibility with the epoxy compound and a weight average molecular weight of 30,000 or more is used, its added amount is preferably 10 parts by mass or more and preferably 40 parts by mass or less based on 100 parts by mass of the resin constituting the adhesive layer.

[0475] If it is 10 parts by mass or more, it is easy to achieve the improvement of flexibility, improvement of viscosity and / or depression suppression of the phase with epoxy compound as the main component (hereinafter referred to as epoxy compound phase), and the insulation is not easily reduced. If it is 40 parts by mass or less, the Tg of the epoxy compound phase is improved.

[0476] The weight average molecular weight of the high molecular weight epoxy compound is preferably 20,000 to 500,000. In this range, the strength and / or flexibility in a sheet state and / or a film state are improved, and tackiness is easily suppressed.

[0477] The polyamide-imide resin, modified polyamide-imide resin, and epoxy compound that are preferably used for the adhesive layer may be used alone or in combination of two or more.

[0478] Furthermore, the compounds may be prepared as a mixture in a varnish state in which the compounds are dissolved in a solvent. By directly applying the mixture on a support such as a PET film and drying the solvent, the compound can be formed into a film and used as an adhesive layer.

[0479] (Silane coupling agent)

[0480] In order to optimize the interfacial bonding between dissimilar materials, a silane coupling agent may be compounded in the adhesive layer.

[0481] Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0482] Among them, γ-mercaptopropyltrimethoxysilane or γ-aminopropyltriethoxysilane is preferred from the viewpoint of adhesive strength.

[0483] When the pressure-sensitive adhesive layer contains a silane coupling agent, the amount thereof blended is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the compound having adhesiveness, from the viewpoint of the effect due to addition and / or the influence on heat resistance.

[0484] (Bulking Agent)

[0485] The adhesive layer may contain a filler (preferably an inorganic filler).

[0486] The adhesive layer containing a filler can improve the handling properties and thermal conductivity of the adhesive layer, and can also impart flame retardancy, adjust melt viscosity, impart thixotropy, and / or enhance surface hardness.

[0487] When the adhesive layer contains a filler, the content thereof is not particularly limited, but preferably the content is 20 to 50 parts by volume based on 100 parts by volume of the compound having adhesiveness contained in the adhesive layer.

[0488] From the viewpoint of the compounding effect, the above content is more preferably 30 parts by volume or more. Furthermore, from the viewpoint of optimizing the storage elastic modulus of the adhesive, improving adhesion and / or suppressing the decrease in insulation by achieving void suppression, the above content is also preferably 50 parts by volume or less.

[0489] Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, aluminum borate whiskers, boron nitride, crystalline silica, amorphous silica, silicon nitride, talc, mica, and barium sulfate.

[0490] Among them, aluminum oxide, boron nitride, or aluminum nitride is preferred because of its high thermal conductivity and good heat dissipation, easy control of impurities, and excellent heat resistance and insulation properties.

[0491] The filler may be used alone or in combination of two or more.

[0492] The average particle size of the filler contained in the adhesive layer is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.2 to 5 μm, from the viewpoint of thermal conductivity.

[0493] From the viewpoint of balancing adhesion and thermal conductivity, the content of the filler in the adhesive layer is preferably 50% by volume or less (eg, 20% by volume or more and 50% by volume or less) relative to the total volume of the adhesive layer.

[0494] In particular, from the viewpoint of bonding strength and thermal conductivity, it is preferred that the adhesive layer contains at least one selected from the group consisting of epoxy compounds and modified polyamide-imide resins as an adhesive compound, contains at least one selected from the group consisting of aluminum oxide and silicon oxide as a filler, the content of the filler is greater than 25 parts by volume and less than 100 parts by volume relative to 100 parts by volume of the adhesive compound, and the average particle size of the filler is 0.2 to 5 μm.

[0495] From the viewpoint of thermal conductivity and adhesiveness, the thickness of the adhesive layer is preferably 1 to 16 μm, more preferably 2 to 15 μm, further preferably 3 to 14 μm, and particularly preferably 4 to 12 μm.

[0496] The film thickness of the adhesive layer can be measured using a micrometer, a stylus film thickness gauge, a pin film thickness gauge, or the like.

[0497] <Adhesive layer>

[0498] The material of the adhesive layer can be used without particular limitation as long as it has the heat resistance and thermal conductivity required of various adhesives and / or thermosetting materials, etc. In addition, an adhesive layer can be used in which the thermal conductivity is improved by mixing various thermal conductive fillers.

[0499] Examples of the adhesive that forms the adhesive layer include acrylic adhesives, olefin adhesives, silicone adhesives, natural rubber adhesives, and synthetic rubber adhesives.

[0500] When used near semiconductors in electronic devices, acrylic adhesives or olefin adhesives are preferred from the viewpoint of less prone to outgassing. Also, silicone adhesives containing silicone resin as a main raw material are preferred from the viewpoint of heat resistance.

[0501] Furthermore, the “adhesive containing a silicone resin as a main raw material” refers to an adhesive containing 60% by mass or more (preferably 80% by mass or more) of a silicone resin.

[0502] As adhesives with silicone resin as the main raw material, for example, peroxide crosslinking (curing) type silicone adhesives and addition reaction type silicone adhesives can be cited. Among them, addition reaction type silicone adhesives are preferred from the viewpoint of high thickness accuracy when set as a thin layer and easy formation of an adhesive layer by transfer method.

[0503] Examples of the addition reaction type silicone adhesive include adhesives containing silicone rubber and silicone resin and, if necessary, additives such as crosslinking agents, fillers, plasticizers, antioxidants, antistatic agents and / or colorants (pigments, dyes, etc.).

[0504] The silicone rubber is not particularly limited as long as it is a silicone rubber component, but preferably contains an organosilanone having a phenyl group (especially an organosilanone having methylphenylsiloxane as a main constituent unit). Various functional groups such as vinyl groups can be introduced into the organosilanone in the silicone rubber as needed.

[0505] The silicone resin is not particularly limited as long as it is a silicone resin used in a silicone adhesive. For example, a silicone resin comprising an organosilane having a constituent unit selected from the group consisting of "R3SiO 1 / 2 ", a unit composed of the constituent unit "SiO2", a unit composed of the constituent unit "RSiO 3 / 2 " and a (co)polymer of at least any one unit in the group of units composed of the constituent unit "R2SiO". In addition, R in the above-mentioned constituent units represents a hydrocarbon group or a hydroxyl group.

[0506] Examples of acrylic pressure-sensitive adhesives include homopolymers and copolymers of (meth)acrylic acid and / or (meth)acrylic acid esters.

[0507] Among them, acrylic adhesives are preferably poly(meth)acrylate polymer compounds containing butyl acrylate or 2-ethylhexyl acrylate as a main raw material component, from the viewpoint of excellent flexibility, chemical stability, processability and / or controllability of adhesiveness.

[0508] The polymer compound preferably has a copolymer structure in which one or more monomers selected from butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate are copolymerized with acrylic acid, acrylonitrile and / or hydroxyethyl acrylate, and polar groups such as -COOH, -CN and -OH are introduced.

[0509] Furthermore, a cross-linked structure can be introduced into the acrylic pressure-sensitive adhesive within a range that does not impair flexibility.

[0510] By introducing a cross-linked structure, it is easy to improve long-term adhesion retention and film strength. For example, a cross-linked structure can be introduced into a polymer having a polar group such as an -OH group by reacting a compound having a plurality of functional groups such as an isocyanate group or an epoxy group bonded to the polar group with the polar group.

[0511] Example

[0512] Below, the present invention is further described in detail based on embodiment.The material, usage amount, ratio, processing content and processing step etc. shown in the following embodiment can be appropriately changed as long as it does not depart from the purpose of the present invention.Thereby, the scope of the present invention should not be interpreted in a limited manner by the embodiment shown below.

[0513] 〔Preparation and evaluation of compositions〕

[0514] [Various ingredients]

[0515] Hereinafter, various components used in Examples and Comparative Examples are shown.

[0516] <Phenol compounds>

[0517] The phenol compounds used in Examples and Comparative Examples are shown below.

[0518] In addition, the phenol compound A-1 used in the examples was synthesized with reference to the specification of US Pat. No. 4,992,596.

[0519] [Chemical formula 12]

[0520]

[0521] <Epoxy compounds>

[0522] The epoxy compounds used in Examples and Comparative Examples are shown below.

[0523] In addition, the following B-2 is a mixture of two epoxy compounds (product name: Epototo ZX-1059, manufactured by Tohto Kasei Co., Ltd.).

[0524] [Chemical formula 13]

[0525]

[0526] <Inorganic substances (inorganic nitrides and other inorganic substances)>

[0527] Inorganic substances used in Examples and Comparative Examples are shown below.

[0528] "AA-3:" Alumina (average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd.)

[0529] "AA-04:" Alumina (average particle size: 0.4 μm, manufactured by Sumitomo Chemical Co., Ltd.)

[0530] "PTX-60:" Agglomerated boron nitride (average particle size: 60 μm, manufactured by Momentive)

[0531] "HP40 MF100:" Agglomerated boron nitride (average particle size: 40 μm, manufactured by Mizushima Ferroalloy Co., Ltd.)

[0532] "SP-3:" scaly boron nitride (average particle size: 4 μm, manufactured by Denka Company Limited.)

[0533] <Curing accelerator>

[0534] As a curing accelerator, PPh3 (triphenylphosphine) was used.

[0535] <Solvent>

[0536] As the solvent, cyclopentanone was used.

[0537] <Dispersant>

[0538] As the dispersant, DISPERBYK-106 (polymer salt having an acidic group) was used.

[0539] <Surface modifier for alumina (organosilane molecule)>

[0540] As the surface modifier for aluminum oxide, the following compounds were used.

[0541] [Chemical formula 14]

[0542]

[0543] <Surface modifiers for inorganic nitrides>

[0544] The surface modifiers for inorganic nitrides (specific compounds or comparative compounds) used in Examples and Comparative Examples are shown below. C-1 to C-25 are specific compounds, and D-1 to D-5 are compounds not corresponding to specific compounds (comparative compounds).

[0545] [Chemical formula 15]

[0546]

[0547] [Chemical formula 16]

[0548]

[0549] [Chemical formula 17]

[0550]

[0551] [Chemical formula 18]

[0552]

[0553] [Chemical formula 19]

[0554]

[0555] [Preparation of composition]

[0556] A curing liquid was prepared by blending the epoxy compound and the phenol compound in the combination shown in Table 1 below in the addition amount (g) described in Table 1.

[0557] After all the amounts 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 order, 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 CORPORATION, Awatori Rentaro ARE-310) to obtain the composition (composition for forming a thermally conductive material) of each example or comparative example.

[0558] The amount of the solvent added is such that the solid content concentration of the composition becomes 50 to 80% by mass.

[0559] In addition, the solid content concentration of each composition was adjusted within the above range so that the viscosity of the composition would be approximately the same.

[0560] The amount of the curing accelerator added was set to an amount such that the content of the curing accelerator in the composition was 1% by mass based on the total content of the epoxy compound and the specific compound having an epoxy group.

[0561] The amount of inorganic substances added (the total amount of inorganic nitride and other inorganic substances added) was set to the amount (g) shown in Table 1.

[0562] In addition, the inorganic substances were mixed and used so that the content ratio (mass ratio) of each inorganic substance satisfied the relationship shown in Table 1.

[0563] The amount of the dispersant added was set to an amount such that the content of the dispersant in the composition was 0.2% by mass relative to the content of the inorganic substance.

[0564] The amount of the surface modifier for alumina added was set to an amount such that the content of the surface modifier for alumina in the composition was 0.2 mass % relative to the content of alumina (total content of AA-3 and AA-04). In addition, when the composition did not contain alumina, the surface modifier for alumina was not used.

[0565] The addition amount of the surface modifier for inorganic nitride (specific compound or comparative compound) was set to the addition amount (g) shown in Table 1.

[0566] [evaluate]

[0567] <Thermal conductivity>(Manufacturing of thermal conductive sheet)

[0568] The prepared composition was uniformly applied on a release surface of a release-treated polyester film (NP-100A manufactured by Annak Co., Ltd., film thickness 100 μm) using an applicator and allowed to stand at 120° C. for 5 minutes to obtain a coating film.

[0569] Two sheets of such coated polyester films were prepared, and after laminating the two sheets of coated polyester films to each other on the coated surface, they were heat-pressed in air (processed at a hot plate temperature of 65°C and a pressure of 12 MPa for 1 minute) to obtain a semi-cured film. The obtained semi-cured film was heat-pressed in air (processed at a hot plate temperature of 160°C and a pressure of 12 MPa for 20 minutes, and then further processed at 180°C under normal pressure for 90 minutes) to cure the coating and obtain a resin sheet. The polyester films on both sides of the resin sheet were peeled off to obtain a thermally conductive sheet with an average film thickness of 200 μm.

[0570] (Manufacturing of thermally conductive multilayer sheets)

[0571] Preparation of adhesive layer film 1: epoxy adhesive layer, no filler

[0572] An adhesive layer coating liquid was obtained by mixing 21.6 parts by mass of B-3 as an epoxy compound, 13.3 parts by mass of A-1 as a phenol compound, 0.21 parts by mass of PPh3 (triphenylphosphine) as a curing accelerator, and 64.9 parts by mass of cyclopentanone.

[0573] The prepared adhesive layer coating liquid was evenly applied on the release surface of a release-treated polyester film (NP-100A manufactured by Pannak Co., Ltd., film thickness 100 μm) using an applicator and left at 120° C. for 5 minutes to obtain a coating film. The final adhesive layer thickness was 5 μm.

[0574] Preparation of adhesive layer film 2: epoxy adhesive layer, with filler

[0575] A coating liquid for an adhesive layer was obtained by mixing 21.6 parts by mass of B-3 as an epoxy compound, 13.3 parts by mass of A-1 as a phenol compound, 0.21 parts by mass of PPh3 as a curing accelerator, 35 parts by mass of alumina AA-04, and 100 parts by mass of cyclopentanone.

[0576] The prepared adhesive layer coating liquid was evenly applied on the release surface of a release-treated polyester film (NP-100A manufactured by Annak Co., Ltd., film thickness 100 μm) using an applicator and left at 120° C. for 5 minutes to obtain a coating film. The final thickness of the adhesive layer was 5 μm.

[0577] Preparation of adhesive layer film 3: acrylic copolymer resin, no filler

[0578] A mixed solvent of methylethyl copper and toluene was used to test an acrylic copolymer resin (HTR-280DR, manufactured by Nagase Chemtex Corporation, butyl acrylate / acrylonitrile / acrylic acid copolymer, Mw: 900,000, Tg: -30.9°C, volume resistivity>10 13 Ω·m, 15 mass % toluene solution) to obtain a pressure-sensitive adhesive layer coating liquid.

[0579] The prepared adhesive layer coating liquid was evenly applied on the release surface of a release-treated polyester film (NP-100A manufactured by Pannak Co., Ltd., film thickness 100 μm) using an applicator and left at 120° C. for 5 minutes to obtain a coating film. The final adhesive layer thickness was 5 μm.

[0580] In addition, the layer formed by the above-mentioned acrylic ester copolymer resin is an adhesive layer, but for convenience, it is called an adhesive layer in the examples of this specification.

[0581] ·Multilayer film production

[0582] A semi-cured film (a semi-cured film having polyester films on both sides) was obtained by the same procedure as described above (Production of Thermally Conductive Sheet).

[0583] The polyester films provided on both sides of the semi-cured film were peeled off, and the adhesive layer films were overlapped respectively in a manner that the adhesive layer and the semi-cured film were opposite to each other. The adhesive layers were bonded using a laminating machine under the conditions of temperature 120°C, pressure 0.7MPa, vacuum degree ≤1kPa, and time 15 seconds, thereby obtaining a multilayer sheet having an adhesive coating on both sides of the semi-cured film.

[0584] ·Production of multi-layer cured products

[0585] The obtained multilayer sheet was heat-pressed in air (after being 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. under normal pressure for 90 minutes) to cure the coating film and the semi-cured film and obtain a resin sheet. The polyester films on both sides of the resin sheet were peeled off to obtain a multilayer sheet cured product (thermally conductive multilayer sheet) with an average film thickness of 200 μm.

[0586] The thermal conductivity of each thermally conductive sheet or thermally conductive multilayer sheet obtained using each composition was evaluated. The thermal conductivity was measured by the following method, and the thermal conductivity was evaluated according to the following criteria.

[0587] (Measurement of Thermal Conductivity (W / m·K)) (1) Using "LFA467" manufactured by NETZSCH JAPAN KK, the thermal diffusivity in the thickness direction of the thermally conductive sheet was measured by a laser flash method.

[0588] (2) The specific gravity of the thermally conductive sheet or the thermally conductive multilayer sheet was measured using a balance "XS204" manufactured by Mettler Toledo International Inc. by the Archimedean method (using a "solid specific gravity measurement kit").

[0589] (3) Using "DSC320 / 6200" manufactured by Seiko Instruments Inc., the specific heat of the thermally conductive sheet or thermally conductive multilayer sheet at 25°C was determined under the temperature increase condition of 10°C / min.

[0590] (4) The thermal conductivity of the thermally conductive sheet or the thermally conductive multilayer sheet was calculated by multiplying the obtained thermal diffusivity by the specific gravity and specific heat.

[0591] (Evaluation Criteria)

[0592] The measured thermal conductivity was classified according to the following criteria and used as the evaluation of thermal conductivity.

[0593] “A+”: 15W / m·K or above

[0594] "A": 10W / m·K or more and less than 15W / m·K

[0595] "B:" 8W / m·K or more and less than 10W / m·K

[0596] "C:" 5W / m·K or more and less than 8W / m·K

[0597] "D:" less than 5W / m·K

[0598] Table 1 shows the results.

[0599] <Surface shape (smoothness) of sheet>

[0600] A thermally conductive sheet or a thermally conductive multilayer sheet was produced in the same manner as in the production in the above-mentioned <Thermal Conductivity> test, and the surface shape (smoothness) of the sheet was evaluated.

[0601] Specifically, the film thickness of the thermally conductive sheet or thermally conductive multilayer sheet was measured at any five locations, and the standard deviation of the measurement deviation was calculated and evaluated according to the following criteria. When the standard deviation is small (in other words, when the deviation of the film thickness is small), it can be evaluated that the surface shape (smoothness) of the sheet is good.

[0602] In addition, if the surface shape (smoothness) of the sheet is good, it means that the inorganic substance (especially inorganic nitride) is well dispersed. On the other hand, if the standard deviation is large (in other words, if the deviation of the film thickness is large), it means that aggregation occurs in the cured product and surface irregularities are generated, that is, the dispersibility of the inorganic substance (especially inorganic nitride) is poor.

[0603] The film thickness measurement was performed using “Ai-Phase·Mobile 1u” manufactured by ai-Phase Co. Ltd.

[0604] (Evaluation Criteria)

[0605] The obtained standard deviations were classified according to the following criteria and used as the evaluation of the surface shape (smoothness) of the sheet.

[0606] "A:" standard deviation is less than 5μm

[0607] "B:" Standard deviation is 5 μm or more and less than 10 μm

[0608] "C:" Standard deviation is 10 μm or more and less than 30 μm

[0609] "D:" Standard deviation is 30μm or more

[0610] Table 1 shows the results.

[0611] [result]

[0612] Table 1 below shows the types and addition amounts (g) of the phenol compound, epoxy compound, inorganic substance, and inorganic nitride surface modifier used in each composition, and the evaluation results.

[0613] In Table 1, the column "Hydroxyl content" shows the hydroxyl content (mmol / g) of the phenol compound used.

[0614] The column of "specific functional group" shows the type of the specific functional group possessed by the specific compound used. In addition, the description of "epoxy group" in the column of "specific functional group" means "monovalent group having an epoxy group".

[0615] In Table 1, the "Adhesive layer" column indicates whether the test body (thermal conductive sheet or thermal conductive multilayer sheet) has an adhesive layer. The record "None" indicates that the test body is a thermal conductive sheet without an adhesive layer. The record "1" indicates that the test body is a thermal conductive multilayer sheet having an adhesive layer formed using adhesive layer film 1. The record "2" indicates that the test body is a thermal conductive multilayer sheet having an adhesive layer formed using adhesive layer film 2. The record "3" indicates that the test body is a thermal conductive multilayer sheet having an adhesive layer formed using adhesive layer film 3.

[0616] [Table 1]

[0617]

[0618] [Table 2]

[0619]

[0620] [Table 3]

[0621]

[0622]

[0623] The results shown in the table confirm that a thermally conductive material having excellent thermal conductivity can be obtained by using the composition of the present invention, and that the surface shape of a thermally conductive sheet obtained by using the composition is also improved.

[0624] It was confirmed that when the composition contained a phenol compound having a hydroxyl content of 8.0 mmol / g or more, the thermal conductivity of the obtained thermally conductive material was more excellent (comparison between Examples 93 to 104 and Examples 69 to 80, etc.).

[0625] It was confirmed that when the content of the inorganic substance contained in the composition is 85 mass % or less relative to the solid content of the composition, the surface shape of the obtained thermally conductive sheet is more excellent (comparison between Examples 3 and 2, comparison between Examples 9 and 8, etc.).

[0626] It was confirmed that when the composition contained both a phenol compound and an epoxy compound, the thermal conductivity of the obtained thermally conductive material was more excellent when the specific compound had at least one of an aldehyde group and a boric acid group and a hydroxyl group (comparison of Examples 25 to 32 with Examples 7 and 13 to 24, etc.).

[0627] It was confirmed that when the content of the specific compound was 0.05 mass % or more relative to the total solid content, the thermal conductivity of the obtained thermally conductive material was more excellent (comparison between Examples 4 and 5, comparison between Examples 10 and 11, etc.).

[0628] It was confirmed that when the specific compound is "a compound containing only a monovalent group having an epoxy group as a specific functional group" or "a compound containing only a hydroxyl group as a specific functional group", and when the content of the specific compound is 0.5 mass % or more relative to the content of the inorganic nitride, the thermal conductivity of the obtained thermally conductive material is further excellent (comparison of Examples 25 to 33 with Examples 34 to 41, etc.).

Claims

1. A composition comprising an inorganic nitride, a compound represented by the general formula (1-2) or (1-3), an epoxy compound and a phenol compound, The hydroxyl content of the phenol compound is 8.0 mmol / g or more, In the general formula (1-2) or the general formula (1-3), E 1 ~E 3 Each independently represents -NH-, g 1 ~g 3 Each independently represents an integer of 0 or 1, Z 1 a~Z 1 c. Z 2 a~Z 2 c and Z 3 a~Z 3 c each independently represents a hydrogen atom or a group represented by the general formula (2), wherein: Z 1 a~Z 1 c. Z 2 a~Z 2 c and Z 3 a~Z 3 In c, a total of 2 or more groups are represented by the general formula (2), In the general formula (2), * represents the bonding position, D 1 represents a single bond or a divalent connecting group, A 1 represents an aromatic ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms, or represents a cycloalkyl ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms, Q and Y 1 each independently represents a specific functional group selected from the group consisting of an aldehyde group, a boronic acid group, a hydroxyl group, a monovalent group having an epoxy group, an amino group, a thiol group, a carboxylic acid group, a monovalent group having a carboxylic anhydride group, an isocyanate group, and a monovalent group having an oxetane group, p represents an integer greater than 0, q represents an integer from 0 to 2, In the general formula (2), D 1 If there are multiple D 1 They can be the same or different. 1 If there are multiple A 1 can be the same or different. If there are multiple Qs, the multiple Qs can be the same or different. 1 If there are multiple Y 1 They may be the same or different. When there are multiple ps, the multiple ps may be the same or different. When there are multiple qs, the multiple qs may be the same or different.

2. A composition comprising an inorganic nitride and a compound represented by the general formula (1-2) or the general formula (1-3), and contains an epoxy compound and substantially no phenol compound, wherein the content of the compound represented by the general formula (1-2) or the general formula (1-3) is 5% by mass or more relative to the total solid content of the composition, or The phenol compound is contained, the epoxy compound is substantially not contained, and the content of the compound represented by the general formula (1-2) or the general formula (1-3) is 5% by mass or more relative to the total solid content of the composition, In the general formula (1-2) or the general formula (1-3), E 1 ~E 3 Each independently represents -NH-, g 1 ~g 3 Each independently represents an integer of 0 or 1, Z 1 a~Z 1 c. Z 2 a~Z 2 c and Z 3 a~Z 3 c each independently represents a hydrogen atom or a group represented by the general formula (2), wherein: Z 1 a~Z 1 c. Z 2 a~Z 2 c and Z 3 a~Z 3 In c, a total of 2 or more groups are represented by the general formula (2), In the general formula (2), * represents the bonding position, D 1 represents a single bond or a divalent connecting group, A 1 represents an aromatic ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms, or represents a cycloalkyl ring group which may have a substituent and has 6 or more carbon atoms as ring-constituting atoms, Q and Y 1 each independently represents a specific functional group selected from the group consisting of an aldehyde group, a boronic acid group, a hydroxyl group, a monovalent group having an epoxy group, an amino group, a thiol group, a carboxylic acid group, a monovalent group having a carboxylic anhydride group, an isocyanate group, and a monovalent group having an oxetane group, p represents an integer greater than 0, q represents an integer from 0 to 2, In the general formula (2), D 1 If there are multiple D 1 They can be the same or different. 1 If there are multiple A 1 can be the same or different. If there are multiple Qs, the multiple Qs can be the same or different. 1 If there are multiple Y 1 They may be the same or different. When there are multiple ps, the multiple ps may be the same or different. When there are multiple qs, the multiple qs may be the same or different.

3. The composition according to claim 2, wherein contains the phenol compound and substantially does not contain the epoxy compound, The phenol compound has a hydroxyl content of 8.0 mmol / g or more.

4. The composition according to claim 2, wherein contains the epoxy compound and substantially does not contain the phenol compound, The epoxy compound has an epoxy group content of 4.0 mmol / g or more.

5. The composition according to any one of claims 1 to 4, wherein Q and Y 1 Each independently represents a group selected from the group consisting of an aldehyde group, a boronic acid group, a hydroxyl group, and a monovalent group having an epoxy group.

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

7. The composition according to any one of claims 1 to 4, further comprising a curing accelerator.

8. The composition according to any one of claims 1 to 4, wherein The inorganic nitride is boron nitride.

9. The composition according to any one of claims 1 to 4, wherein The composition further comprises other inorganic substances other than the inorganic nitride, and the total content of the inorganic nitride and the other inorganic substances is 70 to 85% by mass relative to the total solid content of the composition; or The composition does not contain the other inorganic substance, and the content of the inorganic nitride is 70 to 85% by mass based on the total solid content of the composition.

10. The composition according to any one of claims 1 to 4, wherein In the general formula (1-2) or (1-3), Z 1 a~Z 1 c. Z 2 a~Z 2 c and Z 3 a~Z 3 One or more of c are each independently a group represented by the general formula (2) having at least one functional group selected from the group consisting of an aldehyde group and a boronic acid group. 11 . The composition according to claim 1 , which is a composition for forming a thermally conductive material. 12 . A thermally conductive sheet formed by curing the composition according to claim 1 .

13. A thermally conductive multilayer sheet comprising: The thermally conductive sheet according to claim 12; and An adhesive layer or a pressure-sensitive adhesive layer is disposed on one or both sides of the thermally conductive sheet.

14. A device with a heat-conducting layer, comprising: Devices; and A heat-conducting layer disposed on the device, the heat-conducting layer comprising the heat-conducting sheet according to claim 12 or the heat-conducting multilayer sheet according to claim 13.

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