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WO2022054874A1 - Composition de résine durcissable, matériau thermoconducteur, feuille thermoconductrice, et dispositif à couche thermoconductrice - Google Patents

Composition de résine durcissable, matériau thermoconducteur, feuille thermoconductrice, et dispositif à couche thermoconductrice Download PDF

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Publication number
WO2022054874A1
WO2022054874A1 PCT/JP2021/033173 JP2021033173W WO2022054874A1 WO 2022054874 A1 WO2022054874 A1 WO 2022054874A1 JP 2021033173 W JP2021033173 W JP 2021033173W WO 2022054874 A1 WO2022054874 A1 WO 2022054874A1
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WIPO (PCT)
Prior art keywords
group
epoxy
compound
epoxy compound
heat conductive
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Ceased
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PCT/JP2021/033173
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English (en)
Japanese (ja)
Inventor
誠一 人見
慶太 高橋
大介 林
輝樹 新居
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022547651A priority Critical patent/JPWO2022054874A1/ja
Publication of WO2022054874A1 publication Critical patent/WO2022054874A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H10W40/10—
    • H10W40/25—

Definitions

  • the present invention relates to a curable resin composition, a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer.
  • Patent Document 1 describes an insulating thermal conductivity containing a predetermined (meth) acrylic copolymer, which is a copolymer of a (meth) acrylic monomer and glycidyl methacrylate, and a thermally conductive filler. The sheet is disclosed.
  • the heat conductive material is also required to be able to firmly adhere to the object (adhesive material) that transfers heat, and the peel (peeling) strength of the heat conductive material to the adherend may be sufficiently high. It has been demanded.
  • the present inventors examined the insulating heat conductive sheet described in Patent Document 1, it was confirmed that there is room for improvement in the peel strength of the formed insulating heat conductive sheet with respect to the adherend.
  • Another object of the present invention is to provide a curable resin composition capable of providing a heat conductive material having excellent peel strength. Another object of the present invention is to provide a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer relating to the curable resin composition.
  • a curable resin composition containing a phenol compound, a first epoxy compound, a second epoxy compound, and an inorganic substance. Satisfying at least one of the requirements that the phenol compound contains a phenol compound having a triazine skeleton and that the first epoxy compound contains an epoxy compound having a triazine skeleton.
  • the second epoxy compound is a curable resin composition which is an acrylic resin having an epoxy group in a side chain.
  • [3] The curable resin composition according to [1] or [2], wherein the inorganic substance contains aggregated boron nitride having an average particle size of 20 ⁇ m or more.
  • the first epoxy compound is a polyhydroxybenzene type epoxy compound, an epoxy compound having a biphenyl skeleton, a bisphenol F type epoxy compound, a phenol novolac type epoxy compound, a phenoxy resin, and an epoxy compound represented by the general formula (E2).
  • C represents a carbon atom.
  • U represents an integer of 3 or 4.
  • V represents a substituent or a hydrogen atom having no epoxy group.
  • W represents an epoxy-containing group.
  • the epoxy-containing group is a group that is an epoxy group itself, or a monovalent group that contains an epoxy group as a part.
  • a plurality of Ws existing in the general formula (E2) may be the same or different from each other.
  • a curable resin composition capable of providing a heat conductive material having excellent peel strength. Further, according to the present invention, it is possible to provide a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer relating to the curable resin composition.
  • the curable resin composition the heat conductive material, the heat conductive sheet, and the device with the heat conductive layer of the present invention will be described in detail.
  • the description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • (meth) acryloyl group means “either one or both of acryloyl group and methacryloyl group”.
  • (meth) acrylamide group means “either one or both of an acrylamide group and a methacrylamide group”.
  • (meth) acrylic means “either one or both of acrylic and methacrylic”.
  • the acid anhydride group may be a monovalent group or a divalent group.
  • the acid anhydride group represents a monovalent group, a substitution obtained by removing an arbitrary hydrogen atom from an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride.
  • the group is mentioned.
  • the acid anhydride group represents a divalent group, the group represented by * -CO-O-CO- * is intended (* represents a bond position).
  • substituents and the like that do not specify substitution or non-substitution if possible, further substituents (for example, a group of substituents described later) are added to the groups as long as the desired effect is not impaired.
  • Y may be possessed.
  • alkyl group means a substituted or unsubstituted alkyl group (an alkyl group which may have a substituent) as long as the desired effect is not impaired.
  • the type of the substituent, the position of the substituent, and the number of the substituents in the case of "may have a substituent” are not particularly limited. Examples of the number of substituents include one or two or more.
  • substituent examples include a monovalent non-metal atomic group excluding a hydrogen atom, and a group selected from the following substituent group Y is preferable.
  • halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
  • Substituent group Y Halogen atoms (-F, -Br, -Cl, -I, etc.), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate base groups, anhydrous carboxylic acid groups, cyanate ester groups, unsaturated polymerizable groups, epoxy groups, oxetanyl Group, aziridinyl group, thiol group, isocyanate group, thioisocyanate group, aldehyde group, alkoxy group, allyloxy group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, N-alkylamino group, N, N-dialkylamino Group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ary
  • sulfinamoyl group N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfina Moil group, sulfamoyl group, N-alkyl sulfamoyl group, N, N-dialkyl sulfamoyl group, N-aryl sulfamoyl group, N, N-diaryl sulfamoyl group, N-alkyl-N-arylsul Famoyl group, N-acylsulfamoyl group and its conjugated base group, N-alkylsulfonylsulfamoyl group (-SO 2 NHSO 2 (alkyl)) and its conjugated base group, N-arylsulfon
  • each of the above-mentioned groups may further have a substituent (for example, one or more groups among the above-mentioned groups), if possible.
  • a substituent for example, one or more groups among the above-mentioned groups
  • an aryl group which may have a substituent is also included as a group selectable from the substituent group Y.
  • the number of carbon atoms of the group is, for example, 1 to 20.
  • the number of atoms other than the hydrogen atom of the group selected from the substituent group Y is, for example, 1 to 30.
  • these substituents may or may not form a ring by bonding with each other or with a group to be substituted, if possible.
  • the alkyl group (or the alkyl group moiety in a group containing an alkyl group as a partial structure, such as an alkoxy group) may be a cyclic alkyl group (cycloalkyl group) and has one or more cyclic structures as a partial structure. It may be an alkyl group.
  • composition The curable resin composition of the present invention (hereinafter, also simply referred to as “composition”) is a curable resin composition containing a phenol compound, a first epoxy compound, a second epoxy compound, and an inorganic substance. , Satisfying at least one of the requirements that the phenol compound contains a phenol compound having a triazine skeleton and that the first epoxy compound contains an epoxy compound having a triazine skeleton.
  • the second epoxy compound is a curable resin composition which is an acrylic resin having an epoxy group in a side chain.
  • the composition of the present invention contains a second epoxy compound which is an acrylic resin having an epoxy group in the side chain. Such a second epoxy compound exhibits good adhesion to the adherend. Further, in addition to the second epoxy compound, the composition of the present invention also contains a phenol compound which is a compound having a triazine skeleton and / or the first epoxy compound described above.
  • the composition of the present invention comprises a phenolic compound.
  • the phenol compound is a compound having 1 or more (preferably 2 or more, more preferably 2 to 10) hydroxyl groups directly bonded to the aromatic ring group. Above all, the phenol compound preferably has a triazine skeleton.
  • a phenol compound means having one or more (for example, 1 to 5) triazine ring groups in the compound.
  • the phenol compound is preferably a compound represented by the general formula (Z).
  • E 1 to E 6 independently represent a single bond, -NH-, or -NR-.
  • R represents a substituent.
  • the substituent represented by R include a linear or branched alkyl group having 1 to 5 carbon atoms.
  • E 1 to E 6 are preferably -NH- or -NR-, and more preferably -NH-.
  • B 1 represents a single bond or a k + 1 valent organic group.
  • B 2 represents a single bond or an l + 1 valent organic group.
  • B 3 represents a single bond or m + 1 valent organic group.
  • B 4 represents a single bond or an n + 1 valent organic group.
  • the values of k, l, m, and n in the above-mentioned k + 1-valent organic group, l + 1-valent organic group, m + 1-valent organic group, and n + 1-valent organic group are specified in the general formula (Z). , K, l, m, and n.
  • the value of m in the m + 1 valent organic group represented by B 3 indicates the number of X 3 to which the B 3 is bonded. Is the same as the value of.
  • Examples of the organic group represented by B 1 to B 4 include a group obtained by removing j hydrogen atoms from a hydrocarbon group which may have a hetero atom having 1 to 20 carbon atoms.
  • j means k + 1, l + 1, m + 1, or n + 1.
  • the hydrocarbon group before removing j hydrogen atoms may have, for example, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. Examples thereof include one or more groups selected from the group consisting of an aliphatic ring group having 3 to 20 carbon atoms and an aromatic ring group having 3 to 20 carbon atoms which may have a substituent.
  • the group further consists of -O-, -S-, -CO-, -NR N- ( RN is a hydrogen atom or a substituent), and -SO 2- . It may be a group consisting of a combination of one or more of the selected divalent linking groups.
  • Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methane, ethane, propane, butane, pentane, hexane, and heptane.
  • Examples of the aliphatic ring group having 3 to 20 carbon atoms include a cyclohexane ring group, a cycloheptane ring group, a norbornane ring group, and an adamantane ring group.
  • Examples of the aromatic ring group having 3 to 20 carbon atoms include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring and the like, and examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include a furan ring and a pyrrole ring. , Thiophene ring, pyridine ring, thiazole ring, carbazole ring, indole ring, benzothiazole ring and the like.
  • k, l, m, and n each independently represent an integer of 0 or more.
  • the total of k, l, r ⁇ m, and n is 2 or more, preferably an integer of 2 to 12, and more preferably an integer of 4 to 8.
  • the value of m in "r ⁇ m" is an average value of m that may exist in a plurality of values.
  • k, l, m, and n are preferably 0 to 5, and more preferably 1 to 2.
  • k is preferably 1 or more (for example, 1 to 2)
  • l is preferably 1 or more (for example, 1 to 2)
  • m is preferably 1 or more (for example, 1 to 2).
  • n is 1 or more (for example, 1 to 2).
  • B 1 does not have X 1 .
  • B 2 does not have X 2 .
  • m does not have X 3 .
  • B 4 does not have X 4 .
  • B 1 is a single bond
  • k is 1.
  • B 2 is a single bond
  • l is 1.
  • B 3 is a single bond
  • m is 1.
  • B 4 is a single bond
  • n is 1.
  • L represents a divalent organic group.
  • the organic group include an aromatic ring group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, and-. Examples thereof include O-, -S-, -N (RN)-, -CO-, and a group combining these.
  • RN represents a substituent. Examples of the substituent represented by RN include a linear or branched alkyl group having 1 to 5 carbon atoms. Further, examples of the substituent which the aromatic ring group, the aliphatic hydrocarbon group and the aliphatic ring group may have include a linear or branched alkyl group having 1 to 5 carbon atoms. Can be mentioned.
  • Examples of the aromatic ring group include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a monocyclic aromatic ring group such as a benzene ring; a polycyclic aromatic ring group such as a naphthalene ring and an anthracene ring; and the like, and the number of carbon atoms is high.
  • Examples of the 3 to 20 aromatic heterocyclic groups include monocyclic aromatic ring groups such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, and a thiazole ring; a benzothiazole ring, a carbazole ring, and an indole ring. Etc., Polycyclic aromatic ring groups; and the like.
  • As the aromatic ring group as L a group obtained by removing two hydrogen atoms from the above example can be mentioned.
  • Examples of the aliphatic hydrocarbon group include an alkylene group having 1 to 12 carbon atoms, and specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and a methylhexylene group. , And a heptylene group and the like.
  • Examples of the aliphatic ring group include a cyclohexane ring group, a cycloheptane ring group, a norbornane ring group, an adamantane ring group and the like.
  • As the aliphatic ring group as L a group obtained by removing two hydrogen atoms from the above example can be mentioned.
  • An aromatic ring group which may have a substituent an aliphatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, or -O-, -S.
  • a group in which -, -NR N- or -CO- is combined not only a divalent linking group consisting of a combination of two or more of these, but also a group of the same type (for example, an aromatic ring group) is connected via a single bond. It may be a divalent linking group in which two or more are combined.
  • L in the above general formula (P2) may have a divalent aromatic ring group or a substituent which may have a substituent. It is a divalent organic group having at least one selected from the group consisting of a divalent aliphatic ring group which may have and an alkylene group which may have a branch having 2 or more carbon atoms. It is preferable, and a divalent organic group having a divalent aromatic ring group which may have a substituent may be more preferable because the thermal conductivity is more excellent.
  • r is an integer of 0 or more. r is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.
  • X 1 to X 4 each independently represent an aromatic ring group having a phenolic hydroxyl group.
  • the "aromatic ring group having a phenolic hydroxyl group” may be any aromatic ring group having one or more (for example, 1 to 4) hydroxyl groups (phenolic hydroxyl groups) directly bonded to the aromatic ring.
  • the aromatic ring group may or may not have a substituent other than the hydroxyl group.
  • the aromatic ring group may be monocyclic or polycyclic, and may have a heteroatom as a ring member atom.
  • the number of ring member atoms of the aromatic ring group is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6.
  • the aromatic ring group is preferably a benzene ring group.
  • a substituent that the aromatic ring group may have other than the hydroxyl group a substituent having 1 to 6 carbon atoms is preferable, a hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a linear chain having 1 to 6 carbon atoms is more preferable. Alternatively, a branched alkyl group is more preferable.
  • k X 1 , l X 2 , r ⁇ m X 3 , and n X 4 is a phenolic hydroxyl group. It is also preferable that the aromatic ring group has a substituent arranged at the ortho position of the phenolic hydroxyl group. The substituent may be present in only one of the ortho positions of the phenolic hydroxyl group, or may be present in both.
  • the value of m in "r ⁇ m" is an average value of m that may exist in a plurality of values.
  • the "substituted group arranged at the ortho position” is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and a linear or branched chain having 1 to 6 carbon atoms.
  • Alkyl groups in the form are more preferable.
  • the aromatic ring groups other than the "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group” are It may or may not have a substituent other than a hydroxyl group (phenolic hydroxyl group).
  • the aromatic ring group other than the "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group” include a hydroxyphenyl group.
  • aromatic ring groups having phenolic hydroxyl groups represented by any of X 1 to X 4
  • at least one is “phenolic hydroxyl group and phenol”. It is also preferable that it is an aromatic ring group other than the "aromatic ring group having a substituent arranged at the ortho position of the sex hydroxyl group”.
  • aromatic ring groups having phenolic hydroxyl groups represented by X 1 to X 4 there are also aromatic ring groups other than "aromatic ring groups having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group”. It is considered that the symmetry of the compound as a whole is broken, the melting point of the compound is lowered, and the handleability of the semi-cured film formed from the composition is improved.
  • the phenol compound is also preferably a compound represented by the general formula (Z1).
  • the phenol compound preferably contains a compound represented by the general formula (Z1), and the phenol compound may be the compound itself represented by the general formula (Z1).
  • the content of the compound represented by the general formula (Z1) is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, still more preferably 50 to 100% by mass, based on the total mass of the phenol compound.
  • r represents an integer of 0 or more. r is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.
  • L represents a divalent organic group.
  • the divalent organic group represented by L in the general formula (Z1) is, for example, the same as the divalent organic group represented by L in the general formula (Z1).
  • R Z represents a hydrogen atom or a substituent.
  • the substituent represented by RZ is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and a linear or linear group having 1 to 6 carbon atoms. It is more preferably a branched alkyl group.
  • At least one (preferably 30% or more, more preferably 50% or more, still more preferably 65% or more, preferably 90% or less, more preferably 80) of (3 + r) RZs present in the general formula (Z1). % Or less) may represent a substituent.
  • At least one (for example, 1 to 2) of R Z existing in (3 + r) in the general formula (Z1) may represent a hydrogen atom.
  • the above R z (preferably R z which is a substituent) is bonded to the above benzene ring group. It is also preferable that it exists in the para position with respect to NH.
  • the phenol compound is also preferably a compound represented by the general formula (Z2).
  • the phenol compound preferably contains a compound represented by the general formula (Z2), and the phenol compound may be the compound itself represented by the general formula (Z2).
  • the content of the compound represented by the general formula (Z2) is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, still more preferably 50 to 100% by mass, based on the total mass of the phenol compound.
  • R Z represents a hydrogen atom or a substituent. It is also preferable that at least one of the two RZs represents a substituent, and it is also preferable that both represent a substituent.
  • the substituent represented by RZ is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is even more preferable.
  • the alkyl group may be linear or branched. It is also preferable that the alkyl group is unsubstituted.
  • the two Rz in the general formula (Z2) may be the same or different from each other.
  • phenol compounds include, for example, benzene polyols such as benzenediol or benzenetriol, biphenylaralkyl type phenol resin, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, and dicyclopentadienephenol addition type.
  • Resin phenol aralkyl resin, polyvalent phenol novolac resin synthesized from polyhydric hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol phenol co-condensed novolak resin, naphthol.
  • Cresol co-condensed novolak resin biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, alkoxy group-containing aromatic ring-modified novolak resin and the like are also preferable.
  • the molecular weight of the phenol compound is preferably 225 to 2000, more preferably 225 to 1000.
  • the molecular weight is a weight average molecular weight.
  • the hydroxyl group content of the phenol compound is preferably 2.0 mmol / g or more, more preferably 4.0 mmol / g or more.
  • the upper limit is preferably 25.0 mmol / g or less, more preferably 10.0 mmol / g or less.
  • the hydroxyl group content is intended to be the number of hydroxyl groups (preferably phenolic hydroxyl groups) possessed by 1 g of the phenol compound.
  • the phenol compound may have an active hydrogen-containing group (carboxylic acid group or the like) capable of polymerizing with an epoxy compound (first epoxy compound and second epoxy compound) in addition to the hydroxyl group. You don't have to.
  • the lower limit of the active hydrogen content (total content of hydrogen atoms in hydroxyl groups, carboxylic acid groups, etc.) of the phenol compound is preferably 2.0 mmol / g or more, and more preferably 4.0 mmol / g or more.
  • the upper limit is preferably 25.0 mmol / g or less, more preferably 10.0 mmol / g or less.
  • the composition of the present invention is a compound having a group capable of reacting with an epoxy compound (first epoxy compound and second epoxy compound) (also referred to as “other active hydrogen-containing compound”). May include.
  • the mass ratio of the content of other active hydrogen-containing compounds to the content of the phenol compound is preferably 0 to 1, more preferably 0 to 0.1, and 0 to 0.05. Is more preferable.
  • the composition of the present invention comprises a first epoxy compound.
  • the epoxy compound is a compound having at least one epoxy group (oxylanyl group) in one molecule and does not correspond to the second epoxy compound described later.
  • the epoxy group is a group obtained by removing one or more hydrogen atoms (preferably one hydrogen atom) from the oxylan ring. If possible, the epoxy group may further have a substituent (a linear or branched alkyl group having 1 to 5 carbon atoms, or the like).
  • the number of epoxy groups contained in the first epoxy compound is preferably 2 or more, more preferably 2 to 1000, and even more preferably 2 to 40 in one molecule.
  • the molecular weight of the first epoxy compound is preferably 150 or more, more preferably 300 or more.
  • the upper limit of the molecular weight is not limited, and for example, 100,000 or less is preferable, and 10,000 or less is more preferable.
  • the molecular weight is a weight average molecular weight.
  • the number average molecular weight and the weight average molecular weight are the weight average molecular weights obtained in terms of polystyrene by gel permeation chromatography (GPC).
  • the epoxy group content of the first epoxy compound is preferably 2.0 to 20.0 mmol / g, more preferably 5.0 to 15.0 mmol / g.
  • the epoxy group content is intended to be the number of epoxy groups contained in 1 g of the epoxy compound.
  • the first epoxy compound also preferably has an aromatic ring group (preferably an aromatic hydrocarbon ring group).
  • the first epoxy compound may or may not exhibit liquid crystallinity. That is, the first epoxy compound may be a liquid crystal compound. In other words, it may be a liquid crystal compound having an epoxy group.
  • the first epoxy compound (which may be a liquid crystal epoxy compound) include a compound having at least a rod-like structure (rod-like compound) and a compound having at least a disk-like structure (disk). State compound).
  • the rod-shaped compound and the disk-shaped compound will be described in detail.
  • Examples of the first epoxy compound which is a rod-shaped compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano-substituted phenylpyrimidines. Examples thereof include alkoxy-substituted phenylpyrimidines, phenyldioxans, trans, and alkenylcyclohexylbenzonitriles. Not only low molecular weight compounds as described above, but also high molecular weight compounds can be used.
  • the polymer compound is a polymer compound obtained by polymerizing a rod-shaped compound having a low molecular weight reactive group.
  • Preferred rod-shaped compounds include rod-shaped compounds represented by the following general formula (XXI).
  • Q 1 and Q 2 are independent epoxy groups, and L 111 , L 112 , L 113 , and L 114 independently represent a single bond or a divalent linking group, respectively. ..
  • a 111 and A 112 each independently represent a divalent linking group (spacer group) having 1 to 20 carbon atoms.
  • M represents a mesogen group.
  • the epoxy groups of Q1 and Q2 may or may not have a substituent.
  • L 111 , L 112 , L 113 , and L 114 each independently represent a single bond or a divalent linking group.
  • the divalent linking groups represented by L 111 , L 112 , L 113 , and L 114 are independently -O-, -S-, -CO-, -NR 112- , and -CO-O, respectively.
  • R 112 is an alkyl group or a hydrogen atom having 1 to 7 carbon atoms.
  • L 113 and L 114 are preferably —O— independently of each other.
  • L 111 and L 112 are preferably single bonds independently of each other.
  • a 111 and A 112 each independently represent a divalent linking group having 1 to 20 carbon atoms.
  • the divalent linking group may contain heteroatoms such as non-adjacent oxygen and sulfur atoms.
  • an alkylene group, an alkenylene group, or an alkynylene group having 1 to 12 carbon atoms is preferable.
  • the above-mentioned alkylene group, alkenylene group, or alkynylene group may or may not have an ester group.
  • the divalent linking group is preferably linear, and the divalent linking group may or may not have a substituent.
  • substituents examples include a halogen atom (fluorine atom, chlorine atom, and bromine atom), a cyano group, a methyl group, and an ethyl group.
  • a 111 and A 112 are each independently preferably an alkylene group having 1 to 12 carbon atoms, and more preferably a methylene group.
  • M represents a mesogen group, and examples of the mesogen group include known mesogen groups. Of these, a group represented by the following general formula (XXII) is preferable.
  • W 1 and W 2 independently represent a divalent cyclic alkylene group, a divalent cyclic alkaneylene group, an arylene group, or a divalent heterocyclic group, respectively.
  • L 115 represents a single bond or a divalent linking group.
  • n represents an integer of 1 to 4.
  • W 1 and W 2 examples include 1,4-cyclohexenediyl, 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-zyl.
  • W 1 and W 2 may each have a substituent.
  • substituents include the groups exemplified in the above-mentioned substituent group Y, and more specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), cyano group, and carbon.
  • An alkyl group having a number of 1 to 10 for example, a methyl group, an ethyl group, a propyl group, etc.
  • an alkoxy group having 1 to 10 carbon atoms for example, a methoxy group, an ethoxy group, etc.
  • a group having 1 to 10 carbon atoms for example, formyl group, acetyl group, etc.
  • Acrylic group eg, formyl group, acetyl group, etc.
  • alkoxycarbonyl group having 1 to 10 carbon atoms eg, methoxycarbonyl group, ethoxycarbonyl group, etc.
  • acyloxy group having 1 to 10 carbon atoms eg, ethoxycarbonyl group, etc.
  • Acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like can be mentioned.
  • the plurality of W 1s may be the same or different from each other.
  • L 115 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L 115 include the above-mentioned divalent linking groups represented by L 111 to L 114 , and examples thereof include -CO-O- and -O-CO-. , -CH 2 -O-, and -O-CH 2- .
  • the plurality of L 115s may be the same or different from each other.
  • the preferred skeleton of the basic skeleton of the mesogen group represented by the above general formula (XXII) is illustrated below.
  • the above-mentioned mesogen groups may be substituted with a substituent in these skeletons.
  • the biphenyl skeleton is preferable in that the obtained heat conductive material has more excellent heat conductivity.
  • the compound represented by the general formula (XXI) can be synthesized by referring to the method described in JP-A No. 11-513019 (WO97 / 00600).
  • the rod-shaped compound may be a monomer having a mesogen group described in JP-A No. 11-323162 and Japanese Patent No. 4118691.
  • the rod-shaped compound is preferably a compound represented by the general formula (E1).
  • LE1 independently represents a single bond or a divalent linking group. Of these, LE1 is preferably a divalent linking group.
  • the alkylene group may be linear, branched or cyclic, but a linear alkylene group having 1 to 2 carbon atoms is preferable.
  • a plurality of LE1s may be the same or different from each other.
  • LE2 is preferably single-bonded, -CO-O-, or -O-CO- independently of each other. When there are a
  • LE3 is a 5-membered or 6-membered aromatic ring group or a 5-membered or 6-membered ring which may independently have a single bond or a substituent. Represents a non-aromatic ring group or a polycyclic group composed of these rings. Examples of the aromatic ring group and the non-aromatic ring group represented by LE3 include 1,4-cyclohexanediyl group, 1,4-cyclohexendyl group and 1,4-phenylene which may have a substituent.
  • pyrimidin-2,5-diyl group pyridine-2,5-diyl group, 1,3,4-thiadiazol-2,5-diyl group, 1,3,4-oxadiazole-2,5-diyl
  • examples thereof include a group, a naphthalene-2,6-diyl group, a naphthalene-1,5-diyl group, a thiophene-2,5-diyl group, and a pyridazine-3,6-diyl group.
  • a transformer body is preferable.
  • LE3 is preferably a single bond, a 1,4-phenylene group, or a 1,4-cyclohexenediyl group.
  • the substituent of the group represented by LE3 is 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 1 carbon number). preferable.
  • the substituents may be the same or different.
  • the plurality of LE3s may be the same or different.
  • pe represents an integer of 0 or more.
  • pe is an integer of 2 or more, a plurality of ( -LE3 - LE2- ) may be the same or different from each other.
  • pe is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • LE4 independently represents a substituent.
  • the substituent an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or an acetyl group are preferable, and an alkyl group (preferably 1 carbon number) is more preferable.
  • a plurality of LE4s may be the same or different from each other. Further, when le described below is an integer of 2 or more, a plurality of LE4s existing in the same ( LE4 ) le may be the same or different.
  • le independently represents an integer of 0 to 4. Among them, le is preferably 0 to 2 independently of each other. A plurality of le may be the same or different from each other.
  • one or both of the two existing "epoxy groups-LE1-" are replaced with diglycidylaminoalkylene groups (preferably diglycidyl aminomethylene groups). Is also preferable.
  • the rod-shaped compound preferably has a biphenyl skeleton in that the obtained heat conductive material has better heat conductivity.
  • the first epoxy compound preferably has a biphenyl skeleton, and in this case, the first epoxy compound is more preferably a rod-shaped compound.
  • the first epoxy compound which is a disc-shaped compound, has a disc-shaped structure at least partially.
  • the disk-like structure has at least an alicyclic or aromatic ring.
  • the disk-shaped compound can form a columnar structure by forming a stacking structure by ⁇ - ⁇ interaction between molecules.
  • Angew. Chem. Int. Ed. examples thereof include the triphenylene structure described in 2012, 51, 7990-7793 or JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-002220 and JP-A-2010-2440338.
  • a heat conductive material showing high heat conductivity can be obtained.
  • the rod-shaped compound can conduct heat only linearly (one-dimensionally), whereas the disk-shaped compound can conduct heat planarly (two-dimensionally) in the normal direction, so that the heat conduction path is It is thought that the number will increase and the thermal conductivity will improve.
  • the disk-shaped compound preferably has three or more epoxy groups.
  • a cured product of a composition containing a disk-shaped compound having three or more epoxy groups tends to have a high glass transition temperature and high heat resistance.
  • the number of epoxy groups contained in the disk-shaped compound is preferably 8 or less, and more preferably 6 or less.
  • disk-shaped compound examples include C.I. Destrade et al. , Mol. Crysr. Liq. Cryst. , Vol. 71, page 111 (1981); Chemical Society of Japan, Quarterly Review of Chemistry, No. 22, Liquid crystal chemistry, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al. , Angew. Chem. Soc. Chem. Comm. , Page 1794 (1985); J. Mol. Zhang et al. , J. Am. Chem. Soc. , Vol. In the compounds described in 116, page 2655 (1994), and Japanese Patent No. 4592225, compounds having at least one end (preferably three or more) as an epoxy group can be mentioned.
  • disk-shaped compound examples include Angew. Chem. Int. Ed. Ends in the triphenylene structure described in 2012, 51, 7990-7793, and JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-002220 and JP-A-2010-240383. Examples thereof include compounds in which at least one (preferably three or more) of the above is used as an epoxy group.
  • a compound represented by any of the following formulas (D1) to (D16) is preferable from the viewpoint of better thermal conductivity of the heat conductive material.
  • equations (D1) to (D15) will be described, and then the equation (D16) will be described.
  • "-LQ” represents “-L-Q”
  • QL- represents "QL-”.
  • L represents a divalent linking group.
  • L is independently an alkylene group, an alkaneylene group, an arylene group, -CO-, -NH-, -O-, -S-, and a combination thereof. It is preferable that the group is selected from the group consisting of, and two or more groups are selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O-, and -S-. More preferably, it is a combined group.
  • the alkylene group preferably has 1 to 12 carbon atoms.
  • the number of carbon atoms of the alkenylene group is preferably 2 to 12.
  • the arylene group preferably has 10 or less carbon atoms.
  • the alkylene group, alkenylene group, and arylene group may have a substituent (preferably an alkyl group, a halogen atom, a cyano, an alkoxy group, an acyloxy group, etc.).
  • L is shown below.
  • the bond on the left side binds to the side of the central structure of the compound represented by any of the formulas (D1) to (D15) (hereinafter, also simply referred to as "central ring"), and the bond on the right side.
  • AL means an alkylene group or an alkenylene group
  • AR means an arylene group.
  • the alkylene group represented by AL may be linear or branched, and has, for example, 1 to 12 carbon atoms.
  • the alkenylene group represented by AL may be linear or branched, and has, for example, 2 to 12 carbon atoms.
  • the arylene group represented by AR may be monocyclic or polycyclic, and the number of ring member atoms is preferably 6 to 12.
  • Q independently represents a hydrogen atom or a substituent.
  • substituents include the groups exemplified in the above-mentioned substituent group Y. More specifically, as the substituent, the above-mentioned reactive functional group, halogen atom, isocyanate group, cyano group, unsaturated polymerizable group, epoxy group, oxetanyl group, aziridinyl group, thioisocyanate group, aldehyde group, and Examples include sulfo groups.
  • Q is a group other than the epoxy group, it is preferable that Q is stable with respect to the epoxy group.
  • one or more (preferably two or more) Qs represent an epoxy group. Above all, from the viewpoint of better thermal conductivity of the heat conductive material, it is preferable that all Qs represent epoxy groups.
  • the compounds represented by the formulas (D1) to (D15) preferably do not have -NH- from the viewpoint of the stability of the epoxy group.
  • the compound represented by the formula (D4) is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.
  • the central ring of the disc-shaped compound is preferably a triphenylene ring.
  • the compound represented by the formula (XI) is preferable from the viewpoint of more excellent thermal conductivity of the heat conductive material.
  • R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are independently * -X 11 -L 11 -P 11 or * -X 12 -L, respectively.
  • * represents the bonding position with the triphenylene ring.
  • R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 two or more are * -X 11 -L 11 -P 11 , and three or more are * -X 11 -L. 11 -P 11 is preferable.
  • R 11 and R 12 one or more of R 13 and R 14 , and any one of R 15 and R 16
  • the number is * -X 11 -L 11 -P 11 .
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are all * -X 11 -L 11 -P 11 .
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are all the same.
  • X 11 is independently single-bonded, -O-, -CO-, -NH-, -O-CO-, -O-CO-O-, -O-CO-NH-, -O-CO-.
  • X 11 independently have -O-, -O-CO-, -O-CO-O-, -O-CO-NH-, -CO-O-, -CO-NH-, and -NH.
  • -CO- or -NH-CO-O- is preferable, and -O-, -O-CO-, -CO-O-, -O-CO-NH-, or -CO-NH- is more preferable.
  • -O-CO- or -CO-O- is even more preferred.
  • L 11 independently represents a single bond or a divalent linking group.
  • divalent linking groups include -O-, -O-CO-, -CO-O-, -S-, -NH-, and alkylene groups (preferably 1 to 10 carbon atoms, 1 to 8 carbon atoms). Is more preferable, 1 to 7 is more preferable), an arylene group (the number of carbon atoms is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10), or a group consisting of a combination thereof. Can be mentioned.
  • Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptylene group.
  • Examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group and an anthrasenylene group, and a 1,4-phenylene group is preferable. ..
  • the alkylene group and the arylene group may each have a substituent.
  • the number of substituents is preferably 1 to 3, more preferably 1.
  • the substitution position of the substituent is not particularly limited.
  • As the substituent a halogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. It is also preferable that the alkylene group and the arylene group are unsubstituted. Of these, the alkylene group is preferably unsubstituted.
  • Examples of ⁇ X 11 ⁇ L 11 ⁇ include L101 to L143, which are examples of L described above.
  • P11 represents an epoxy group.
  • the epoxy group may or may not have a substituent.
  • X 12 is the same as X 11 , and the preferred conditions are also the same.
  • L 12 is the same as L 11 , and the preferred conditions are also the same.
  • Examples of ⁇ X 12 ⁇ L 12 ⁇ include L101 to L143, which are examples of L described above.
  • Y 12 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • one or more methylene groups are substituted with -O-, -S-, -NH-, -N (CH 3 )-, -CO-, -O-CO-, or -CO-O-.
  • One Y 12 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • one or more hydrogen atoms contained in Y 12 may be substituted with a halogen atom.
  • the compound represented by the formula (XI) conforms to the methods described in JP-A-7-306317, JP-A-7-281028, JP-A-2005-156822, and JP-A-2006-301614. Can be synthesized.
  • a compound represented by the formula (D16) is also preferable as the disk-shaped compound.
  • R 17X , R 18X , and R 19X each independently represent * -X 211X- (Z 21X -X 212X ) n21X- L 21X -Q. * Represents the position of connection with the central ring.
  • X 211X and X 212X are independently single-bonded, -O-, -CO-, -NH-, -O-CO-, -O-CO-O-, -O-CO-NH-, -O. -CO-S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-, -NH-CO-O-, -NH-CO-NH-, -NH-CO Represents —S—, —S—, —S—CO—, —S—CO—O—, —S—CO—NH—, or —S—CO—S—.
  • Z 21X independently represents a 5- or 6-membered aromatic ring group or a 5-membered or 6-membered non-aromatic ring group, respectively.
  • L 21X represents a single bond or a divalent linking group.
  • Q is synonymous with Q in the formulas (D1) to (D15), and the preferred conditions are also the same.
  • at least one (preferably all) Q among the plurality of Qs present represents an epoxy group.
  • n21X represents an integer of 0 to 3. When n21X is 2 or more, a plurality of (Z 21X -X 212X ) may be the same or different.
  • the compound represented by the formula (D16) As the compound represented by the formula (D16), the compound represented by the formula (XII) is preferable.
  • R 17 , R 18 and R 19 are independently * -X 211- (Z 21 -X 212 ) n21 -L 21 -P 21 or * -X 221- (Z 22 -X 222 ). Represents n22 - Y22 . * Represents the position of connection with the central ring. Two or more of R 17 , R 18 , and R 19 are * -X 211- (Z 21 -X 212 ) n21 -L 21 -P 21 . From the viewpoint of better thermal conductivity of the heat conductive material, R 17 , R 18 and R 19 are all * -X 211- (Z 21 -X 212 ) n21 -L 21 -P 21 . preferable. In addition, it is preferable that R 17 , R 18 , and R 19 are all the same.
  • X 211 , X 212 , X 221 and X 222 are independently single-bonded, -O-, -CO-, -NH-, -O-CO-, -O-CO-O-, -O, respectively.
  • -CO-NH-, -O-CO-S-, -CO-O-, -CO-NH-, -CO-S-, -NH-CO-, -NH-CO-O-, -NH-CO Represents -NH-, -NH-CO-S-, -S-, -S-CO-, -S-CO-O-, -S-CO-NH-, or -S-CO-S-.
  • single bond, -NH-, -O-, -CO-O-, or -O-CO- is preferable, respectively.
  • Z 21 and Z 22 independently represent a 5-membered or 6-membered aromatic ring group or a 5-membered or 6-membered non-aromatic ring group, for example, a benzene ring group (1,4-). Examples thereof include a phenylene group and a 1,3-phenylene group), and an aromatic heterocyclic group.
  • the aromatic ring group and the non-aromatic ring group may have a substituent.
  • the number of substituents is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • the substitution position of the substituent is not particularly limited.
  • a halogen atom or a methyl group is preferable. It is also preferable that the aromatic ring group and the non-aromatic ring group are unsubstituted. Further, as the substituent, it may further have a group represented by "-X 212 -L 21 -P 21 ".
  • aromatic heterocyclic group examples include the following aromatic heterocyclic groups.
  • * represents a site that binds to X 211 or X 221 .
  • ** represents a site that binds to X 212 or X 222 .
  • a 41 and A 42 each independently represent a methine group or a nitrogen atom.
  • X4 represents an oxygen atom, a sulfur atom, or an imino group. It is preferable that at least one of A 41 and A 42 is a nitrogen atom, and it is more preferable that both are nitrogen atoms. Further, X4 is preferably an oxygen atom.
  • n21 and n22 which will be described later, are two or more, a plurality of (Z 21 -X 212 ) and (Z 22 -X 222 ) may be the same or different from each other.
  • L 21 independently represents a single bond or a divalent linking group, and is synonymous with L 11 in the above formula (XI).
  • Examples of L 21 include -O-, -O-CO-, -CO-O-, -S-, -NH-, and an alkylene group (the number of carbon atoms is preferably 1 to 10 and more preferably 1 to 8). ⁇ 7 is more preferable), an arylene group (the number of carbon atoms is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10), or a group composed of a combination thereof is preferable.
  • examples of ⁇ X212 ⁇ L21 ⁇ include L101 to L143, which are examples of L in the above formulas (D1) to (D15).
  • the bond on the left side of L101 to L143 binds to the side of the central structure of the compound (hereinafter, also simply referred to as “central ring”), and the bond on the right side binds to P21.
  • P21 represents an epoxy group.
  • the epoxy group may or may not have a substituent.
  • Each of Y 22 has a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or branched alkyl group having 1 to 20 carbon atoms.
  • one or more methylene groups are -O-, -S-, -NH-, -N (CH 3 )-, -CO-, -O-CO-, or -CO-.
  • n21 and n22 each independently represent an integer of 0 to 3, and an integer of 1 to 3 is preferable from the viewpoint of better thermal conductivity.
  • Preferred examples of the disk-shaped compound include the following compounds.
  • R represents -X 212 -L 21 -P 21 .
  • the compound represented by the formula (XII) can be synthesized according to the methods described in JP-A-2010-244038, JP-A-2006-07692, and JP-A-2007-002220.
  • the disk-shaped compound is preferably a compound having a hydrogen-bonding functional group from the viewpoint of reducing the electron density, strengthening the stacking, and facilitating the formation of a columnar aggregate.
  • Hydrogen-bonding functional groups include -O-CO-NH-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NH-CO-NH-, and -NH-CO-S. -Or-S-CO-NH- and the like can be mentioned.
  • the first epoxy compound has, for example, a phenolic hydroxyl group in the general formula (Z), the general formula (Z1), or the general formula (Z2) described in the description of the phenol compound.
  • a compound represented by a general formula can be used instead of the epoxy-containing group.
  • the epoxy-containing group is a group that is the epoxy group itself, or a monovalent group that contains an epoxy group as a part.
  • the monovalent group containing the epoxy group as a part is a group having one or more (preferably 1 to 8) epoxy groups in the whole group.
  • the monovalent group containing the epoxy group as a part is preferably a group represented by "-(divalent hydrocarbon group) M1- (-O-2-valent hydrocarbon group-) M2 -epoxide group".
  • M1 represents 0 or 1.
  • M2 represents an integer of 1 or more (preferably 1 to 10).
  • the divalent hydrocarbon group may or may not have a substituent, and the divalent hydrocarbon group may further have an epoxy-containing group as a substituent.
  • the divalent hydrocarbon groups that may be present in a plurality thereof may be the same or different from each other.
  • an epoxy compound represented by the general formula (DN) can be mentioned.
  • nDN represents an integer of 0 or more, preferably 0 to 5, and more preferably 1.
  • RDN represents a single bond or a divalent linking group.
  • the divalent linking group includes -O-, -O-CO-, -CO-O-, -S-, an alkylene group (preferably 1 to 10 carbon atoms), and an arylene group (the carbon number is preferably 1 to 10). 6 to 20 is preferable), or a group composed of a combination thereof is preferable, an alkylene group is more preferable, and a methylene group is more preferable.
  • an epoxy compound represented by the general formula (E2) can also be mentioned.
  • C represents a carbon atom.
  • U represents an integer of 3 or 4.
  • "U” in “4-U” indicating the number of V and "U” indicating the number of W show the same value. That is, the general formula (E2) is "VC (-W) 3 " or "C (-W) 4 ".
  • V represents a substituent or a hydrogen atom having no epoxy group.
  • the above-mentioned substituent having no epoxy group is a substituent other than the epoxy group and does not contain an epoxy group as a part of the substituent.
  • the substituent having no epoxy group include a group selected from the substituent group Y, excluding an epoxy group and a group containing an epoxy group as a part.
  • the substituent having no epoxy group is preferably an alkyl group, and more preferably a linear or branched alkyl group.
  • the alkyl group preferably has 1 to 5 carbon atoms.
  • W represents an epoxy-containing group.
  • the epoxy-containing group is a group that is the epoxy group itself, or a monovalent group that contains an epoxy group as a part.
  • the monovalent group containing the epoxy group as a part is a group having one or more (preferably 1 to 8) epoxy groups in the whole group.
  • the monovalent group containing the epoxy group as a part is preferably a group represented by "-(divalent hydrocarbon group) M1- (-O-2-valent hydrocarbon group-) M2 -epoxide group".
  • M1 represents 0 or 1.
  • M2 represents an integer of 1 or more (preferably 1 to 10).
  • the divalent hydrocarbon group may or may not have a substituent, and the divalent hydrocarbon group may further have an epoxy-containing group as a substituent.
  • the divalent hydrocarbon groups that may be present in a plurality thereof may be the same or different from each other.
  • a plurality of Ws existing in the general formula (E2) may be the same or different from each other.
  • Examples of the other first epoxy compound include compounds in which the epoxy group is fused. Examples of such a compound include 3,4: 8,9-diepoxybicyclo [4.3.0] nonane and the like.
  • first epoxy compounds include, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, and bisphenol AD, which are glycidyl ethers such as bisphenol A, F, S, and AD.
  • Type epoxy compound, etc . hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol AD type epoxy compound, etc .
  • phenol novolac type glycidyl ether phenol novolak type epoxy compound), cresol novolak type glycidyl ether (cresol novolak type epoxy compound) ), Bisphenol A novolak 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
  • the first epoxy is a compound in which one or more of the glycidyl ether group and / or the glycidyl ester group in each of the above compounds is replaced with a diglycidylamino group or a diglycidylaminoalkylene group (diglycidylaminomethylene group, etc.). It may be used as a compound.
  • Each of the above compounds may have a substituent.
  • the aromatic ring group, cycloalkane ring group, and / or alkylene group contained in each of the above compounds is other than the glycidyl ether group, the glycidyl ester group, the diglycidyl amino group, and / or the diglycidyl aminoalkylene group. It may have a substituent of.
  • the first epoxy compound a polyhydroxybenzene type epoxy compound, an epoxy compound having a biphenyl skeleton, a bisphenol F type epoxy compound, a phenol novolac type epoxy compound, a phenoxy resin, or .
  • the first epoxy compound may be the above-mentioned one or more kinds of epoxy compounds themselves, or may be contained in a part thereof.
  • the content of the above-mentioned one or more kinds of epoxy compounds is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 90 to 100% by mass, based on the total mass of the first epoxy compound.
  • composition of the present invention at least one of the fact that the phenol compound contains a phenol compound having a triazine skeleton (Requirement 1) and that the first epoxy compound contains an epoxy compound having a triazine skeleton (Requirement 2). Meet the requirements.
  • the composition may satisfy only Requirement 1, only Requirement 2, or both Requirement 1 and Requirement 2.
  • the compound and the first epoxy compound "have a triazine skeleton"
  • the compound has one or more (for example, 1 to 5) triazine ring groups.
  • the phenol compound having a triazine skeleton include the above-mentioned compound represented by the general formula (Z), the compound represented by the general formula (Z1), and the compound represented by the general formula (Z2). Be done.
  • a compound in which A 2 , A 3 , and A 4 are all ⁇ N in the compound represented by the above, and represented by the general formula (Z) in which the phenolic hydroxyl group is replaced with an epoxy group-containing group.
  • the content thereof is more than 0% by mass and 100% by mass or less with respect to the total mass of the phenol compound, and is 30 to 100. It is preferably by mass, more preferably 60 to 100% by mass, still more preferably 90 to 100% by mass.
  • the first epoxy compound contains an epoxy compound having a triazine skeleton (that is, when requirement 2 is satisfied)
  • the content of the phenol compound having a triazine skeleton may be outside the above-mentioned preferable range.
  • the content thereof is more than 0% by mass and 100% by mass or less based on the total mass of the first epoxy compound. It is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 90 to 100% by mass.
  • the phenol compound contains a phenol compound having a triazine skeleton (that is, when requirement 1 is satisfied)
  • the content of the first epoxy compound having a triazine skeleton may be outside the above-mentioned preferable range.
  • the total content of the phenol compound having a triazine skeleton and the first epoxy compound having a triazine skeleton is the total phenol compound and the total first epoxy compound.
  • the total content of it is preferably more than 0% by mass and less than 100% by mass, more preferably 1 to 90% by mass, still more preferably 5 to 80% by mass.
  • the total content of the first epoxy compound and the phenol compound in the composition is preferably 5 to 90% by mass, more preferably 10 to 50% by mass, and 12 to 12 to the total solid content of the composition. 40% by mass is more preferable.
  • the first epoxy compound and / or the phenol compound may be used alone or in combination of two or more.
  • the solid content is intended as a component forming a heat conductive material and does not contain a solvent.
  • the component forming the heat conductive material referred to here may be a component whose chemical structure changes by reacting (polymerizing) when forming the heat conductive material. Further, if it is a component forming a heat conductive material, even if its property is liquid, it is regarded as a solid content.
  • the composition of the present invention comprises a second epoxy compound.
  • the second epoxy compound is an acrylic resin having an epoxy group in the side chain.
  • the second epoxy compound may or may not have a graft structure. Further, the second epoxy compound may or may not have a block structure. The second epoxy compound may have a branch structure or a star structure.
  • the second epoxy compound contains an acrylic repeating unit in the resin, and the acrylic repeating unit is a repeating unit based on (meth) acrylic acid and a repeating unit based on (meth) acrylic acid esters. , Repeating units based on (meth) acrylamides, repeating units based on (meth) acrylic acid halides, and repeating units based on cyanoacrylic acids. Among them, as the acrylic repeating unit, a repeating unit based on (meth) acrylic acid or a repeating unit based on (meth) acrylic acid esters is preferable.
  • the repeating unit when expressed as a repeating unit based on a specific monomer, a repeating unit derived from a specific monomer, or the like, the repeating unit is a repeating unit having a structure in which the specific monomer is polymerized. All you need is. For example, when a repeating unit formed by using a monomer different from a specific monomer is modified or deprotected to obtain a repeating unit having the same structure as a repeating unit having a structure in which a specific monomer is polymerized, this is performed.
  • the obtained repeating unit is also expressed as a repeating unit based on a specific monomer or a repeating unit derived from a specific monomer.
  • the second epoxy compound has an epoxy group in the side chain. That is, the second epoxy compound has a repeating unit with an epoxy group.
  • the repeating unit having an epoxy group may be a part or all of the acrylic repeating unit, or may be a part or all of the repeating unit other than the acrylic repeating unit described later, and at least the acrylic repeating unit. It is preferable that a part of the repeating unit has an epoxy group.
  • the repeating unit having an epoxy group is, for example, a repeating unit based on (meth) acrylic acid esters having an epoxy group and / or (meth) acrylic acid amides having an epoxy group.
  • acrylic repeating unit (acrylic repeating unit having no epoxy group) other than the repeating unit having an epoxy group examples include the repeating unit based on the following monomers. That is, examples of the monomer include (meth) acrylic acid; 2-hydroxyethyl (meth) acrylic acid, 1-hydroxy-2-propyl (meth) acrylic acid, and 2,3-dihydroxypropyl (meth) acrylic acid.
  • N-dimethylacrylic acid amides and other (meth) acrylic acid amides N-dimethylacrylic acid amides and other (meth) acrylic acid amides; (meth) acrylic acid chloride and other acrylic acid halides; methyl cyanoacrylate, ethyl cyanoacrylate, butyl cyanoacrylate, and octyl cyanoacrylate.
  • Cyanoacrylic acids such as, and the like.
  • acrylic repeating unit which is a repeating unit having an epoxy group
  • examples of the acrylic repeating unit include a repeating unit based on the following monomers.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a divalent hydrocarbon group (alkylene group or the like) having 1 to 8 carbon atoms.
  • the second epoxy compound may have a repeating unit other than the acrylic repeating unit.
  • the repeating unit other than the acrylic repeating unit include a repeating unit based on olefin (ethylene and the like), a repeating unit based on styrenes (styrene and the like), and a repeating unit based on maleic anhydride.
  • a part or all of the repeating units other than the acrylic repeating unit may have an epoxy group in the side chain.
  • the second epoxy compound also preferably has a graft structure.
  • the second epoxy compound has a main chain structure having a repeating unit having an epoxy group, and a repeating unit other than the repeating unit having an epoxy group (repeating unit based on olefin, acrylic repeating unit having no epoxy group). It is also preferable to have a side chain which is a polymer composed of a unit and / or a repeating unit based on styrenes having no epoxy group).
  • the content of the acrylic repeating unit in the second epoxy compound is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, and 1 to 20% by mass with respect to the total mass of the second epoxy compound. Is more preferable.
  • the content thereof is preferably 1 to 99% by mass, more preferably 10 to 80% by mass, based on the total mass of the second epoxy compound. It is preferable, and 20 to 70% by mass is more preferable.
  • the content of the repeating unit having an epoxy group (preferably an acrylic repeating unit having an epoxy group) in the second epoxy compound is preferably 1 to 100% by mass with respect to the total mass of the second epoxy compound. 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable.
  • the weight average molecular weight of the second epoxy compound is preferably 1000 to 5000000, more preferably 2000 to 25000000, and even more preferably 7000 to 1000000.
  • the Tg (glass transition temperature) of the second epoxy compound is preferably ⁇ 60 to 130 ° C., more preferably ⁇ 15 to 100 ° C., and even more preferably ⁇ 5 to 80 ° C.
  • the epoxy group content of the second epoxy compound is preferably 0.05 to 20.0 mmol / g, more preferably 0.1 to 10.0 mmol / g, and even more preferably 0.1 to 5.0 mmol / g.
  • the second epoxy compound a commercially available product may be used.
  • Commercially available products include, for example, LOTADER AX series (manufactured by Arkema), Modiper A4100, Modiper A4300, Modiper A4400 (manufactured by NOF), Marproof G series (manufactured by NOF), and Teisan Resin SG-P3 (manufactured by NOF). Nagase ChemteX Co., Ltd.).
  • the content of the second epoxy compound is preferably 1 to 50% by mass, more preferably 2 to 35% by mass, still more preferably 3 to 25% by mass, and 3 to 15% by mass with respect to the total solid content of the composition. % Is particularly preferable.
  • the content of the second epoxy compound is preferably 1 to 200 parts by mass, more preferably 5 to 170 parts by mass, and 10 to 150 parts by mass with respect to 100 parts by mass of the total content of the first epoxy compound and the phenol compound. By mass is more preferred, 10 to 60 parts by mass is even more preferred.
  • the content of the second epoxy compound is preferably 5 to 500 parts by mass, more preferably 10 to 400 parts by mass, still more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the content of the first epoxy compound. ..
  • the second epoxy compound may be used alone or in combination of two or more.
  • the ratio of the number of hydroxyl groups (preferably phenolic hydroxyl groups) contained in the phenol compound to the total number of epoxy groups contained in the first epoxy compound and the second epoxy compound (number of epoxy groups /).
  • the number of hydroxyl groups) is preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and even more preferably 45/55 to 55/45. That is, the ratio of the content of the phenol compound, the first epoxy compound, and the second epoxy compound in the composition is such that the above-mentioned "number of epoxy groups / number of phenolic hydroxyl groups" is within the above range. The ratio is preferable.
  • the epoxy group of the epoxy compound (the first epoxy compound and the second epoxy compound) and active hydrogen active hydrogen derived from a phenolic hydroxyl group may be used, and other active hydrogen-containing compounds may be used.
  • the equivalent ratio (number of epoxy groups / number of active hydrogens) to (which may be active hydrogen) is preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and 45/55 to. 55/45 is more preferred.
  • the composition comprises an inorganic substance.
  • any inorganic substance conventionally used for the inorganic filler of the heat conductive material may be used.
  • the inorganic substance preferably contains an inorganic nitride and / or an inorganic oxide, and more preferably contains at least an inorganic nitride (preferably boron nitride), because the heat conductive material is more excellent in thermal conductivity and insulating property. It is preferable to contain both an inorganic nitride (preferably boron nitride) and an inorganic oxide (preferably aluminum oxide).
  • the shape of the inorganic substance is not particularly limited, and may be in the form of particles, a film, or a plate.
  • Examples of the shape of the particulate inorganic substance include rice granules, spherical shape, cube shape, spindle shape, scaly shape, agglomerated shape, and indefinite shape.
  • the inorganic oxide examples include zirconium oxide (ZrO 2 ), titanium oxide (TIO 2 ), silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), iron oxide (Fe 2 O 3 , FeO, Fe 3 ). O 4 ), copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide (In 2 ).
  • ZrO 2 zirconium oxide
  • TiO 2 titanium oxide
  • silicon oxide SiO 2
  • aluminum oxide Al 2 O 3
  • iron oxide Fe 2 O 3 , FeO, Fe 3
  • O 4 copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide (In 2 ).
  • the inorganic oxide is preferably titanium oxide, aluminum oxide (alumina), or zinc oxide, and more preferably aluminum oxide.
  • the inorganic oxide may be an oxide produced by oxidizing a metal prepared as a non-oxide in an environment or the like.
  • inorganic nitride examples include boron nitride (BN), carbon nitride (C 3 N 4 ), silicon nitride (Si 3 N 4 ), gallium nitride (GaN), indium nitride (InN), and aluminum nitride (AlN).
  • BN boron nitride
  • C 3 N 4 carbon nitride
  • Si 3 N 4 silicon nitride
  • GaN gallium nitride
  • InN indium nitride
  • AlN aluminum nitride
  • the inorganic nitride preferably contains an aluminum atom, a boron atom, or a silicon atom, more preferably aluminum nitride, boron nitride, or silicon nitride, and even more preferably aluminum nitride or boron nitride. It is particularly preferable to contain boron nitride.
  • the size of the inorganic substance is not particularly limited, but the average particle size of the inorganic substance is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less, in that the dispersibility of the inorganic substance is more excellent.
  • the lower limit is not particularly limited, but in terms of handleability, 10 nm or more is preferable, and 100 nm or more is more preferable.
  • the average particle size of the inorganic substance the catalog value is adopted when a commercially available product is used. If there is no catalog value, as the method for measuring the average particle size, 100 inorganic substances are randomly selected, the particle size (major axis) of each inorganic substance is measured, and the arithmetic is performed. Calculate on average.
  • the inorganic substance preferably contains at least one of an inorganic nitride and an inorganic oxide, and more preferably contains at least an inorganic nitride. It may contain both inorganic nitrides and inorganic oxides.
  • the inorganic nitride preferably contains at least one of boron nitride and aluminum nitride, more preferably at least boron nitride, and further preferably at least agglomerated boron nitride having an average particle size of 20 ⁇ m or more. ..
  • the content of the inorganic nitride (preferably boron nitride and / or aluminum nitride, more preferably aggregated boron nitride having an average particle size of 20 ⁇ m or more) in the inorganic substance is 10 to 100% by mass with respect to the total mass of the inorganic substance. Is preferable, 40 to 100% by mass is more preferable, and 60 to 100% by mass is further preferable.
  • As the inorganic oxide aluminum oxide is preferable.
  • the composition is an inorganic substance (preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride) having an average particle size of 20 ⁇ m or more (preferably 30 ⁇ m or more). , More preferably, boron nitride, particularly preferably aggregated boron nitride).
  • the inorganic material contained in the composition (preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride, further preferably boron nitride and / or aluminum nitride) has a substantially average particle size of 20 ⁇ m or more (preferably 30 ⁇ m). It is also preferable that only the inorganic substances of the above) are used.
  • the fact that the inorganic substances are substantially only inorganic substances having an average particle size of 20 ⁇ m or more means that the content of the inorganic substances having an average particle size of 20 ⁇ m or more is more than 99% by mass with respect to the total mass of the inorganic substances.
  • the inorganic substance preferably has an inorganic substance having a different average particle size, for example, both an inorganic substance X having an average particle size of 20 ⁇ m or more and an inorganic substance Y having an average particle size of less than 20 ⁇ m. It is also preferable to include it.
  • the average particle size of the inorganic substance X is preferably 20 to 300 ⁇ m, more preferably 30 to 200 ⁇ m.
  • the average particle size of the inorganic substance Y is preferably 1 nm or more and less than 20 ⁇ m, and more preferably 10 nm or more and 15 ⁇ m or less.
  • the inorganic substance X is preferably an inorganic nitride or an inorganic oxide, more preferably an inorganic nitride, further preferably boron nitride, and particularly preferably agglutinating boron nitride.
  • the inorganic substance Y is preferably an inorganic nitride or an inorganic oxide, more preferably boron nitride or aluminum oxide.
  • the inorganic substance X and the inorganic substance Y one kind may be used alone, or two or more kinds may be used.
  • the mass ratio of the content of the inorganic substance X to the content of the inorganic substance Y is preferably 50/50 to 99/1, and 60/40 to 95/5. Is more preferable.
  • Inorganic substances may be surface-treated.
  • the surface treatment is intended to be a treatment different from the surface modification using a surface modifier described later.
  • a functional group is introduced on the surface of the inorganic substance, and the inorganic substance easily interacts with a phenol compound, an epoxy compound, and / or a surface modifier described later, and is formed as a heat conductive material. It is considered that the thermal conductivity and peel strength of the above are further improved.
  • the surface treatment includes, for example, plasma treatment (vacuum plasma treatment, atmospheric pressure plasma treatment, aqua plasma treatment, etc.), ultraviolet irradiation treatment, corona treatment, electron beam irradiation treatment, ozone treatment, firing treatment, flame treatment, and Oxidizing agent treatment and the like can be mentioned.
  • the oxidizing agent treatment may be carried out under acidic conditions or basic conditions (pH 12 or higher, etc.).
  • the content of the inorganic substance in the composition is preferably 20% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, based on the total solid content of the composition.
  • the upper limit is less than 100% by mass, preferably 95% by mass or less, and more preferably less than 80% by mass.
  • the composition also preferably contains a curing accelerator.
  • the curing accelerator include tris-orthotrilphosphine, triphenylphosphine, boron trifluoride amine complex, and the compounds described in paragraph 0052 of JP2012-06722.
  • tetraphenylphosphonium tetraphenylborate TPP-K
  • tetraphenylphosphonium tetra-p-tolylborate TPP-MK
  • TPP-LA tetra-n-butylphosphonium laurate
  • bis (tetra-n-butylphosphonium) ) Pyromeritate and phosphonium salt-based curing accelerators such as quaternary phosphonium-based compounds (phosphonium salts) such as bis (naphthalen-2,3-dioxy) phenylsilicate adduct of tetraphenylphosphonium can also be mentioned.
  • 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name).
  • the compound described in paragraph 0052 of JP-A-2004-043405 can also be mentioned.
  • the phosphorus-based curing accelerator to which triphenylborane is added to triarylphosphine include the compounds described in paragraph 0024 of JP-A-2014-005382.
  • the curing accelerator preferably contains a compound containing a phosphorus atom, and preferably contains a phosphonium salt.
  • the curing accelerator may be a compound containing a phosphorus atom or a phosphonium salt itself.
  • the content of the compound containing a phosphorus atom or the phosphonium salt is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 80 to 100% by mass, based on the total mass of the curing accelerator.
  • the curing accelerator may be used alone or in combination of two or more.
  • the content of the curing accelerator is preferably 0.002% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.07% by mass or more, based on the total solid content of the composition.
  • the content of the curing accelerator is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, based on the total solid content of the composition.
  • the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and 0, based on the total epoxy compounds (total of the first epoxy compound and the second epoxy compound). It is more preferably .55% by mass or more.
  • the content of the curing accelerator is preferably 40% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total epoxy compound.
  • the composition of the present invention may further contain a surface modifier as a component different from the above-mentioned components.
  • the surface modifier is a component that surface-modifies the above-mentioned inorganic substances.
  • surface modification means a state in which an organic substance is adsorbed on at least a part of the surface of the inorganic substance.
  • the form of adsorption is not particularly limited, and may be in a bonded state. That is, the surface modification also includes a state in which an organic group obtained by desorption of a part of an organic substance is bonded to the surface of the inorganic substance.
  • the bond may be any bond such as a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metal bond.
  • the surface modification may be made to form a monomolecular film on at least a part of the surface.
  • the monolayer is a monolayer formed by chemisorption of organic molecules and is known as Self-Assembled MonoLayer (SAM).
  • SAM Self-Assembled MonoLayer
  • the surface modification may be only a part of the surface of an inorganic substance, or may be the whole.
  • the term "surface-modified inorganic substance” means an inorganic substance that has been surface-modified with a surface modifier, that is, a substance in which an organic substance is adsorbed on the surface of the inorganic substance. That is, in the composition of the present invention, the inorganic substance may constitute a surface-modified inorganic substance (preferably a surface-modified inorganic nitride and / or a surface-modified inorganic oxide) in combination with the surface modifier.
  • a conventionally known surface modifier such as a carboxylic acid such as a long-chain alkyl fatty acid, an organic phosphonic acid, an organic phosphoric acid ester, and an organic silane molecule (silane coupling agent) can be used.
  • a carboxylic acid such as a long-chain alkyl fatty acid, an organic phosphonic acid, an organic phosphoric acid ester, and an organic silane molecule (silane coupling agent)
  • silane coupling agent organic silane molecule
  • the silane coupling agent is, for example, a compound having a hydrolyzable group directly bonded to a Si atom.
  • the hydrolyzable group include an alkoxy group (preferably 1 to 10 carbon atoms) and a halogen atom such as a chlorine atom.
  • the number of hydrolyzable groups directly bonded to the Si atom of the silane coupling agent is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more. There is no upper limit to the above number, for example, 10,000. It is also preferable that the silane coupling agent has a reactive group.
  • the reactive group examples include an epoxy group, an oxetanyl group, a vinyl group, a (meth) krill group, a styryl group, an amino group, an isocyanate group, a mercapto group, and an acid anhydride group.
  • the number of reactive groups contained in the silane coupling agent is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. There is no upper limit to the above number, for example, 10,000.
  • silane coupling agent examples include 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltri.
  • examples thereof include methoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane, and 3-ureidopropyltriethoxysilane.
  • the surface modifier may be used alone or in combination of two or more.
  • the content of the surface modifier is preferably 0.005 to 5% by mass, more preferably 0.05 to 3% by mass, based on the total solid content of the composition.
  • the content of the surface modifier is preferably 0.01 to 10% by mass, more preferably 0.10 to 5% by mass, based on the total inorganic substances.
  • the composition of the present invention may contain an ion scavenger.
  • the ionic scavenger adsorbs ionic impurities in the composition or in the heat conductive material formed with the composition. This makes it possible to maintain good insulation reliability of the heat conductive material even when the heat conductive material absorbs moisture in the composition.
  • the ion scavenger a known one can be used without particular limitation.
  • the ion trapping agent include a cation adsorbent that captures cations by ion exchange, an anion adsorbent that captures anions by ion exchange, and both cations and anions that are captured by ion exchange.
  • inorganic ion adsorbents such as ion trapping agents; triazinethiol compounds; triazineamine compounds; benzoimidazole compounds; benzotriazole compounds; aminotriazole compounds; and bisphenol-based reducing agents.
  • inorganic ion adsorbents such as ion trapping agents; triazinethiol compounds; triazineamine compounds; benzoimidazole compounds; benzotriazole compounds; aminotriazole compounds; and bisphenol-based reducing agents.
  • all or a part of the above-mentioned inorganic substances may also function as an ion scavenger.
  • the inorganic ion adsorbent includes one or more oxides, oxide hydrates, and hydroxides selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. Can be mentioned. Among them, two or more kinds of oxides, oxidative hydrates, or hydroxides selected from the group consisting of bismuth, zirconium, magnesium, and aluminum are preferable, and a three-component system of magnesium, aluminum, and zirconium is preferable. Hydrotalsite, which is a two-component oxide hydrate of oxide, bismuth and zirconium, and a hydroxide containing magnesium and aluminum, is more preferable, and hydrotalcite is further preferable.
  • Examples of the triazine thiol compound include 2-dibutylamino-4,6-dimercapto-s-triazine.
  • Examples of the benzimidazole compound include benzimidazole.
  • Examples of the benzotriazole compound include 1H-benzotriazole, carboxybenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl).
  • Benzotriazole and 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4-tert-octylphenol] can be mentioned.
  • aminotriazole compound examples include 3-amino-1,2,4-triazole and 3,5-diamino-1,2,4-triazole.
  • bisphenol-based reducing agent examples include 2,2'-methylenebis- (4-ethyl-6-t-butylphenol) and 4,4'-butylidenebis- (6-t-butyl-3-methylphenol). Can be mentioned.
  • ion scavenger for example, DHF-4A, DHT-4A, DHT-4A-2, DHT-4C, Kyoward 500, KW-2000, and KW-2100 (trade name, Kyowa).
  • IXE-100, IXE-500, IXE-600, IXE-700F, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS-A2, and IXEPLAS-B1 (trade name, manufactured by Toagosei Co., Ltd.) ); Gisnet DB (trade name, manufactured by Sankyo Pharmaceutical Co., Ltd.); VD-3 and VD-5 (trade name, manufactured by Shikoku Kasei Co., Ltd.); and Yoshinox BB (trade name, manufactured by Yoshitomi Pharmaceutical Co., Ltd.). ..
  • the content of the ion scavenger is, for example, 0.01 to 10% by mass with respect to the total solid content of the composition.
  • the content of such an ion scavenger is preferably larger than the range of this content.
  • the ion scavenger may be used alone or in combination of two or more.
  • the composition may further contain a solvent.
  • the type of solvent is not particularly limited, and it is preferably an organic solvent.
  • the organic solvent include cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane, tetrahydrofuran and the like.
  • the content of the solvent is preferably an amount having a solid content concentration of the composition of 20 to 90% by mass, more preferably 30 to 80% by mass, and more preferably 50 to 80% by mass. Is more preferable.
  • the content of the solvent is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, still more preferably 20 to 50% by mass, based on the total mass of the composition.
  • the method for producing the composition is not particularly limited, and a known method can be adopted.
  • the above-mentioned various components can be mixed and produced.
  • various components may be mixed all at once or sequentially.
  • the method of mixing the components is not particularly limited, and a known method can be used.
  • the mixing device used for mixing is preferably a liquid disperser, for example, a stirrer such as a rotating revolution mixer, a high-speed rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure injection disperser, an ultrasonic disperser, a bead mill, etc. And a homogenizer can be mentioned.
  • the mixing device may be used alone or in combination of two or more. Degassing may be performed before, after, and / or at the same time as mixing.
  • the composition of the present invention is preferably a composition for forming a heat conductive material.
  • the composition of the present invention is cured to obtain a heat conductive material.
  • the curing method of the composition is not particularly limited, but a thermosetting reaction is preferable.
  • the heating temperature during the thermosetting reaction is not particularly limited. For example, it may be appropriately selected in the range of 50 to 250 ° C. Further, when the thermosetting reaction is carried out, heat treatments having different temperatures may be carried out a plurality of times.
  • the curing treatment is preferably performed on a film-like or sheet-like composition. Specifically, for example, the composition may be applied to form a film and a curing reaction may be carried out.
  • the composition When performing the curing treatment, it is preferable to apply the composition on the substrate to form a coating film and then cure. At this time, a different base material may be brought into contact with the coating film formed on the base material, and then the curing treatment may be performed. The cured product (heat conductive material) obtained after curing may or may not be separated from one or both of the substrates. Further, when the curing treatment is performed, the composition may be applied on different substrates to form coating films, and the curing treatment may be performed in a state where the obtained coating films are in contact with each other. The cured product (heat conductive material) obtained after curing may or may not be separated from one or both of the substrates.
  • the curing treatment may be completed when the composition is in a semi-cured state. Further, after the composition is made into a semi-hardened state, a further curing treatment may be carried out to complete the curing.
  • the curing treatment also referred to as "semi-hardening treatment” for bringing the composition into a semi-hardening state and the curing treatment (also referred to as "main curing treatment") for completely curing are divided into separate steps. You may go.
  • a composition is applied onto a substrate to form a coating film, and then the coating film on the substrate is heated without pressure as it is to obtain a semi-cured heat conductive material (“semi-cured”). It may be a "cured film” or a “semi-cured sheet"), or the coating film on the substrate may be heated or the like to form a semi-cured film while being pressed together.
  • the press working may be carried out before or after the above heating or the like, or may be carried out during the press working.
  • the semi-hardening treatment When press working is performed in the semi-hardened film, it may be easy to adjust the film thickness of the obtained semi-hardened film and / or reduce the amount of voids in the semi-hardened film.
  • the semi-hardening treatment may be performed in a state where the coating films formed on different substrates are laminated, or the semi-hardening treatment may be performed without laminating the coating films.
  • the semi-hardening treatment may be carried out in a state where the coating film formed from the composition is further in contact with a material other than the coating film.
  • the obtained semi-cured film may be used as it is as a heat conductive material, or may be used as a completely cured heat conductive material after the semi-hardened film is further subjected to the main curing treatment.
  • the semi-hardened film may be heated as it is without pressure, or may be heated after being pressed or while being pressed.
  • the main curing treatment may be performed in a state where the separate semi-hardened films are laminated, or the main curing treatment may be performed without laminating the semi-hardened films.
  • the main curing treatment may be carried out in a state where the semi-hardened film is arranged so as to be in contact with the device or the like to be used. It is also preferable that the device and the heat conductive material of the present invention are adhered to each other by this curing treatment.
  • the press used for the press processing there are no restrictions on the press used for the press processing that may be performed during the semi-hardening treatment and / or the curing treatment in the main curing treatment, and for example, a flat plate press may be used or a roll press may be used. good.
  • a roll press for example, a substrate with a coating film obtained by forming a coating film on the substrate is sandwiched between a pair of rolls in which two rolls face each other, and the above pair of rolls is used. It is preferable to apply pressure in the film thickness direction of the coated substrate while rotating the substrate to pass the coated substrate.
  • the base material may be present on only one side of the coating film, or the base material may be present on both sides of the coating film.
  • the substrate with a coating film may be passed through the roll press only once or may be passed a plurality of times.
  • the semi-hardening treatment and / or the curing treatment in the main curing treatment or the like only one of the treatment by the flat plate press and the treatment by the roll press may be carried out, or both may be carried out.
  • the shape of the heat conductive material is not particularly limited, and can be molded into various shapes depending on the application.
  • a typical shape of the molded heat conductive material is, for example, a sheet shape. That is, the heat conductive material obtained by using the composition of the present invention is preferably a heat conductive sheet. Further, the thermal conductivity of the heat conductive material obtained by using the composition of the present invention is preferably isotropic rather than anisotropic.
  • the heat conductive material is preferably insulating (electrically insulating).
  • the composition of the present invention is preferably a thermally conductive insulating composition.
  • the volume resistivity of the heat conductive material at 23 ° C. and 65% relative humidity is preferably 10 10 ⁇ ⁇ cm or more, more preferably 10 12 ⁇ ⁇ cm or more, and even more preferably 10 14 ⁇ ⁇ cm or more.
  • the upper limit is not particularly limited, but is usually 10 18 ⁇ ⁇ cm or less.
  • the heat conductive material obtained by using the composition of the present invention can be used as a heat radiating material such as a heat radiating sheet, and can be used for heat radiating applications of various devices. More specifically, a device with a heat conductive layer can be produced by arranging a heat conductive layer containing the heat conductive material of the present invention on the device, and heat generated from the device can be efficiently dissipated by the heat conductive layer.
  • the heat conductive layer may be a heat conductive layer including a heat conductive multilayer sheet described later. Since the heat conductive material obtained by using the composition of the present invention has sufficient heat conductivity and high heat resistance, it is used for various electric devices such as personal computers, general household appliances, and automobiles.
  • the heat conductive material obtained by using the composition of the present invention has sufficient heat conductivity even in a semi-cured state, it reaches light for photocuring such as gaps between members of various devices. It can also be used as a heat radiating material to be placed in areas where it is difficult to make it. In addition, since it has excellent adhesiveness, it can also be used as an adhesive having thermal conductivity.
  • the heat conductive material obtained by using the composition of the present invention may be used in combination with other members other than the members formed from the present composition.
  • the heat conductive material heat conductive sheet or the like
  • a support adhesion material
  • the support include a plastic material, a metal material, and glass.
  • the plastic material include polyester such as polyethylene terephthalate (PET), polycarbonate, acrylic resin, epoxy resin, polyurethane, polyamide, polyolefin, cellulose derivative, and silicone.
  • the metal material include copper and aluminum.
  • the support (adhesive material) is also preferably in the form of a sheet.
  • the film thickness of the sheet-shaped heat conductive material (heat conductive sheet) is preferably 100 to 300 ⁇ m, more preferably 150 to 250 ⁇ m.
  • an adhesive layer and / or an adhesive layer may be combined with the heat conductive material (preferably a heat conductive sheet).
  • the heat conductive material preferably a heat conductive sheet.
  • a heat conductive multilayer sheet having a heat conductive sheet and an adhesive layer or an adhesive layer provided on one side or both sides of the heat conductive sheet may be produced. ..
  • one of the adhesive layer and the pressure-sensitive adhesive layer may be provided on one side or both sides of the heat conductive sheet, respectively, or both may be provided.
  • An adhesive layer may be provided on one surface of the heat conductive sheet, and an adhesive layer may be provided on the other surface. Further, the adhesive layer and / or the adhesive layer may be partially provided on one side or both sides of the heat conductive sheet, or may be provided on the entire surface.
  • the heat conductive material such as the heat conductive sheet may be in a semi-cured state (semi-cured film), and the heat conductive sheet in the heat conductive multilayer sheet may be in a semi-cured state. ..
  • the adhesive layer in the heat conductive multilayer sheet may be in a cured state, a semi-cured state, or an uncured state.
  • MEH-7500 Phenolic compound manufactured by Meiwa Kasei, which does not have a triazine skeleton
  • G2050M Marproof G2050M / weight average molecular weight 200,000 / glass transition point 74 ° C./Polymer A: Weight average molecular weight 130000 / repeating unit based on methyl methacrylate, repeating unit based on 2-ethylhexyl acrylate, repeating unit based on glycidyl methacrylate, respectively, in order. Contains 37% by mass, 33% by mass, and 30% by mass / glass transition point 10 ° C.
  • ⁇ Inorganic matter> The inorganic substances used in Examples and Comparative Examples are shown below.
  • C-1 TPP-MK (Tetraphenylphosphonium Tetra-p-Trillbolate)
  • C-2 Tris-orthotrilphosphine-C-3: Triphenylphosphine-C-4: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole)
  • KBM-573 N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd. was used as a surface modifier.
  • Epoxy compounds (first epoxy compound and second epoxy compound) and phenol compound of the combination shown in Table 1 below are equalized (the number of epoxy groups in the epoxy compound and the number of hydroxyl groups in the phenol compound are equal). ) was prepared. At this time, in the finally obtained composition, the content of the second epoxy compound and the total content of the phenol compound and the first epoxy compound are adjusted to be as shown in Table 1 below. did. (For example, in the composition of Example 1, the content of the second epoxy compound is 5% by mass with respect to the total solid content of the composition, and the total content of the phenol compound and the first epoxy compound is the composition.
  • the composition was such that the first epoxy compound, the second epoxy compound, and the phenol compound were equivalent as a whole).
  • the solid content of the raw material is adjusted so as to be as shown in Table 1 below.
  • SG-P3 used in the composition of Example 21 is distributed in a state where the second epoxy compound (solid content) is dispersed in a solvent, whereas in the composition of Example 21, the second epoxy compound is distributed.
  • the content of (solid content) itself was adjusted to be 5% by mass with respect to the total solid content of the composition).
  • the amount of the solvent added was set so that the solid content concentration of the composition was 50 to 80% by mass.
  • the solid content concentration of the composition was adjusted for each composition within the above range so that the viscosities of the compositions were about the same.
  • the total content (content of the above mixture) of the first epoxy compound and the phenol compound in the composition is the "total amount (% by mass)" column in Table 1 with respect to the total solid content of the composition.
  • the amount shown in is shown in.
  • the amounts of the curing accelerator, the surface modifier, the inorganic nitride, the inorganic oxide, and the second epoxy compound in the composition are each in each mass in Table 1 with respect to the total solid content of the composition.
  • the amount (% by mass) shown in parentheses was used.
  • the polyester film is peeled off from the semi-cured sheet with the polyester film, and the obtained semi-cured sheet is cut into strips of 20 mm ⁇ 60 mm, and the electrolytic copper foil (20 mm ⁇ 100 mm, thickness: 35 ⁇ m) and the aluminum plate (30 mm) which are the adherends are cut out. It was sandwiched between ⁇ 60 mm, thickness: 1 mm).
  • the obtained laminate was heat-pressed under air (hot plate temperature 180 ° C., pressure 20 MPa for 5 minutes, then hot plate temperature 180 ° C., normal pressure for 90 minutes) to obtain a heat conductive sheet.
  • An aluminum base substrate with a copper foil integrated with the adherend was obtained.
  • the copper foil peel strength of the obtained sample was measured by using a digital force gauge (ZTS-200N, manufactured by Imada Co., Ltd.) and a 90-degree peeling test jig (P90-200N-BB, manufactured by Imada Co., Ltd.) to JIS C 6481. It was measured according to the method for measuring the peeling strength in the normal state described in 1.
  • the peeling of the copper foil in the peel strength test was performed at an angle of 90 ° with respect to the aluminum base substrate with the copper foil at a peeling rate of 50 mm / min.
  • peel strength peel strength
  • Table 1 shows the composition of the solid content and the test results of the composition in each Example or Comparative Example.
  • the effect of the present invention is more excellent when the inorganic substance contains both an inorganic substance having an average particle size of 20 ⁇ m or more and an inorganic substance having an average particle size of less than 20 ⁇ m (see the results of Example 2 and the like). ..
  • the first epoxy compound is a polyhydroxybenzene type epoxy compound, an epoxy compound having a biphenyl skeleton, a bisphenol F type epoxy compound, a phenol novolac type epoxy compound, a phenoxy resin, or an epoxy compound represented by the general formula (E2).
  • E2 an epoxy compound represented by the general formula (E2).
  • thermo conductivity of the heat conductive material (heat conductive sheet) obtained by using the composition of the present invention was measured by the method shown below, the heat conductive material produced by using the composition of any of the examples. It was also confirmed that the (heat conduction sheet) had a heat conductivity of 15 W / m ⁇ K or more. As a result, it was confirmed that the heat conductive material obtained by using the composition of the present invention exhibits good heat conductivity.
  • the thermal conductivity of the obtained heat conductive sheet was measured by the following method. (1) Using “LFA467” manufactured by NETZSCH, the thermal diffusivity in the thickness direction of the heat conductive sheet was measured by a laser flash method. (2) The specific gravity of the heat conductive sheet was measured by the Archimedes method (using the “solid specific gravity measurement kit") using the balance "XS204" manufactured by Metler Toledo. (3) Using “DSC320 / 6200” manufactured by Seiko Instruments Inc., the specific heat of the heat conductive sheet at 25 ° C. was determined under the heating condition of 10 ° C./min. (4) The obtained thermal diffusivity was multiplied by the specific gravity and the specific heat to calculate the thermal conductivity of the heat conductive sheet.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine durcissable capable de donner un matériau thermoconducteur ayant une excellente résistance au pelage. L'invention concerne également un matériau thermoconducteur, une feuille thermoconductrice et un dispositif à couche thermoconductrice, qui se rapportent chacun à la composition de résine durcissable. Une composition de résine durcissable selon la présente invention comprend un composé phénol, un premier composé époxy, un second composé époxy et une substance inorganique. La composition de résine durcissable satisfait au moins l'une des exigences ci-dessous : le composé phénol comprend un composé phénol ayant un squelette triazine ; et le premier composé époxy comprend un composé époxy ayant un squelette triazine. Le second composé époxy est une résine acrylique ayant un groupe époxy dans une chaîne latérale de celle-ci.
PCT/JP2021/033173 2020-09-11 2021-09-09 Composition de résine durcissable, matériau thermoconducteur, feuille thermoconductrice, et dispositif à couche thermoconductrice Ceased WO2022054874A1 (fr)

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WO2017195902A1 (fr) * 2016-05-13 2017-11-16 日立化成株式会社 Composition de résine, préimprégné, feuille métallique dotée d'une résine, stratifié, panneau de circuit imprimé, et procédé de production d'une composition de résine
WO2020153205A1 (fr) * 2019-01-23 2020-07-30 富士フイルム株式会社 Composition, feuille thermoconductrice et dispositif équipé d'une couche thermoconductrice
WO2020158259A1 (fr) * 2019-02-01 2020-08-06 富士フイルム株式会社 Composition pour former un matériau conducteur de la chaleur et matériau conducteur de la chaleur

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JP2004214288A (ja) * 2002-12-27 2004-07-29 Lintec Corp チップ用保護膜形成用シート
JP2008277759A (ja) * 2007-04-04 2008-11-13 Sekisui Chem Co Ltd 絶縁性熱伝導シート
JP2009227947A (ja) * 2008-03-25 2009-10-08 Mitsubishi Electric Corp 熱伝導性樹脂組成物、熱伝導性樹脂シート及びパワーモジュール
WO2013031844A1 (fr) * 2011-08-30 2013-03-07 日立化成株式会社 Encre liquide
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WO2020158259A1 (fr) * 2019-02-01 2020-08-06 富士フイルム株式会社 Composition pour former un matériau conducteur de la chaleur et matériau conducteur de la chaleur

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Publication number Priority date Publication date Assignee Title
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CN115073818B (zh) * 2022-06-17 2023-12-26 山东海科创新研究院有限公司 一种导热填料、高导热聚醚砜复合材料及其制备方法

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