WO2022255130A1 - 熱伝導シート、熱伝導シート付きデバイス - Google Patents

熱伝導シート、熱伝導シート付きデバイス Download PDF

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WO2022255130A1
WO2022255130A1 PCT/JP2022/020969 JP2022020969W WO2022255130A1 WO 2022255130 A1 WO2022255130 A1 WO 2022255130A1 JP 2022020969 W JP2022020969 W JP 2022020969W WO 2022255130 A1 WO2022255130 A1 WO 2022255130A1
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thermally conductive
conductive layer
inorganic particles
heat conductive
conductive inorganic
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English (en)
French (fr)
Japanese (ja)
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秀樹 冨澤
優介 畠中
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon

Definitions

  • the present invention relates to a thermally conductive sheet and a device with a thermally conductive sheet.
  • Patent Literature 1 discloses a thermally conductive sheet having multiple layers.
  • the present inventors have studied the heat conductive sheet as described in Patent Document 1 and the like, and found that when the heat conductive sheet is bonded to an object to be bonded at a low pressure (for example, 5 MPa or less), heat It has been found that there is room for improvement in the adhesion of the conductive sheet to the object to be bonded. Moreover, the thermally conductive sheet is also required to exhibit excellent thermal conductivity after the lamination.
  • an object of the present invention is to provide a thermally conductive sheet that exhibits excellent adhesion to an object to be bonded when bonded to the object to be bonded at a low pressure, and exhibits excellent thermal conductivity after bonding.
  • Another object of the present invention is to provide a device with a thermally conductive sheet.
  • a first thermally conductive layer having two main surfaces; a second heat conductive layer disposed only on one of the two main surfaces of the first heat conductive layer; The average film thickness of the first thermally conductive layer is greater than the average film thickness of the second thermally conductive layer,
  • the first thermally conductive layer contains first thermally conductive inorganic particles,
  • the second thermally conductive layer contains second thermally conductive inorganic particles and a curable compound,
  • the content of the first thermally conductive inorganic particles relative to the total area of the first thermally conductive layer is greater than the content of the second thermally conductive inorganic particles relative to the total area of the second thermally conductive layer,
  • the second thermally conductive inorganic particles in the second thermally conductive layer are aggregated boron nitride and have an average aspect ratio of 1.0 to 1.6, and a thermally conductive inorganic material different from the aggregated boron nitride a particle X, and
  • the heat conductive sheet wherein
  • At least one of the first thermally conductive layer and the second thermally conductive layer further comprises a surface modifier; According to any one of [1] to [9], wherein the aggregated boron nitride constitutes surface-modified aggregated boron nitride together with the surface modifier adsorbed on the surface of the aggregated boron nitride.
  • thermal conductive sheet [11] A device with a thermally conductive sheet, comprising a device and the thermally conductive sheet according to any one of [1] to [10] disposed on the device.
  • the heat conductive sheet which is excellent in the adhesiveness with respect to a to-be-bonded material when it is bonded to a to-be-bonded material at a low pressure, and shows the excellent thermal conductivity after bonding can be provided.
  • a device with a thermally conductive sheet can be provided.
  • FIG. 1 is a schematic diagram showing an example of a semiconductor module
  • FIG. 1 is a schematic diagram showing an example of a semiconductor module
  • FIG. 1 is a schematic diagram showing an example of a semiconductor module
  • FIG. 1 is a schematic diagram showing an example of a semiconductor module
  • FIG. 1 is a schematic diagram showing an example of a semiconductor module
  • a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
  • (meth)acryloyl group means “either one or both of an acryloyl group and a methacryloyl group”.
  • the acid anhydride group may be either a monovalent group or a divalent group.
  • the acid anhydride group represents a monovalent group, it includes a substituent obtained by removing any hydrogen atom from acid anhydrides such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and trimellitic anhydride.
  • the acid anhydride group represents a divalent group, it means a group represented by *--CO--O--CO--*. * represents a binding position.
  • the bonding direction of the divalent groups (eg, --COO--, etc.) indicated is not particularly limited unless otherwise specified.
  • the above compounds are "X-O-CO-Z" and "X-CO-O-Z" It may be any of
  • substituents and the like for which substitution or non-substitution is not specified may have further substituents, if possible, to the extent that the intended effect is not impaired.
  • alkyl group means a substituted or unsubstituted alkyl group (an alkyl group that may have a substituent) within a range that does not impair the intended effect.
  • the type of substituent, the position of the substituent, and the number of substituents in the case of "optionally having a substituent” are not particularly limited. Examples of the number of substituents include one and two or more.
  • the types of substituents are not particularly limited, and examples thereof include halogen atoms and alkyl groups. As used herein, halogen atoms include, for example, chlorine, fluorine, bromine and iodine atoms.
  • the heat conductive sheet of the present invention is a first thermally conductive layer having two main surfaces; a second thermally conductive layer disposed only on one of the two major surfaces of the first thermally conductive layer;
  • the average film thickness of the first thermally conductive layer is greater than the average film thickness of the second thermally conductive layer
  • the first thermally conductive layer comprises first thermally conductive inorganic particles
  • the second thermally conductive layer comprises second thermally conductive inorganic particles and a curable compound
  • the content of the first thermally conductive inorganic particles relative to the total area of the first thermally conductive layer is greater than the content of the second thermally conductive inorganic particles relative to the total area of the second thermally conductive layer
  • the second thermally conductive inorganic particles in the second thermally conductive layer are aggregated boron nitride, and thermally conductive inorganic particles X having an average aspect ratio of 1.0 to 1.6 and different from aggregated boron nitride. , including The content of
  • a feature of the thermally conductive sheet of the present invention is that it has a first thermally conductive layer and a second thermally conductive layer.
  • the second thermally conductive layer which is in contact with the object to be laminated, contains not only aggregated boron nitride exhibiting high thermal conductivity, but also thermal conductivity. Since it contains the inorganic particles X, it is also excellent in adhesion to the object to be bonded. Since the first thermally conductive layer contains the first thermally conductive inorganic particles, it exhibits high thermal conductivity. It is presumed that having such two layers provides excellent thermal conductivity and excellent adhesion.
  • the effect of at least one of thermal conductivity and adhesion is more excellent, the effect of the present invention is also said to be more excellent.
  • the heat conductive sheet 10 shown in FIG. 1 has a first heat conductive layer 12 having two main surfaces and a second heat conductive layer 14 arranged on one main surface of the first heat conductive layer 12 . It is arranged only on one main surface of the two main surfaces of the first thermally conductive layer. In other words, the second heat conductive layer is not arranged on the other main surface of the first heat conductive layer 12 .
  • the first thermally conductive layer 12 includes first thermally conductive inorganic particles 16, and the second thermally conductive layer 14 includes second thermally conductive inorganic particles 18 including aggregated boron nitride 20 and thermally conductive inorganic particles X22.
  • the thermally conductive sheet may have other members in addition to the first thermally conductive layer 12 and the second thermally conductive layer 14 .
  • Other members include, for example, a base material to be described later.
  • at least one of the first thermally conductive layer and the second thermally conductive layer further contains a surface modifier,
  • the aggregated boron nitride, together with the surface modifier adsorbed onto the surface of the aggregated boron nitride constitutes a surface-modified aggregated boron nitride. Details will be described later.
  • the members included in the heat conductive sheet are detailed below.
  • the thermally conductive sheet has a first thermally conductive layer with two main surfaces.
  • the first thermally conductive layer is not particularly limited as long as it contains the first thermally conductive inorganic particles.
  • the first thermally conductive layer preferably contains first thermally conductive inorganic particles and a curable compound.
  • the first thermally conductive layer contains first thermally conductive inorganic particles.
  • Examples of the shape of the first thermally conductive inorganic particles include rice grain-like, spherical, cubic, spindle-like, scale-like, aggregated and irregular shapes.
  • Examples of the first thermally conductive inorganic particles include inorganic nitrides and inorganic oxides.
  • inorganic nitrides include boron nitride (BN), carbon nitride ( C3N4 ), silicon nitride ( Si3N4 ), gallium nitride ( GaN ), indium nitride (InN), aluminum nitride ( AlN ), Chromium nitride ( Cr2N ), copper nitride (Cu3N), iron nitride ( Fe4N ), iron nitride ( Fe3N ) , lanthanum nitride (LaN), lithium nitride ( Li3N ), magnesium nitride (Mg 3N 2 ), molybdenum nitride (Mo 2 N), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN
  • the inorganic nitride preferably contains aluminum atoms, boron atoms or silicon atoms, more preferably aluminum nitride, boron nitride or silicon nitride, still more preferably aluminum nitride or boron nitride, and boron nitride. is particularly preferred.
  • Boron nitride includes, for example, cubic boron nitride and hexagonal boron nitride.
  • the shape of boron nitride may be spherical, tabular, scaly, or aggregated, and aggregated boron nitride is preferred.
  • Aggregated boron nitride is secondary aggregated particles formed by aggregating primary particles of boron nitride (for example, scaly boron nitride).
  • inorganic oxides examples include zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), iron oxide (e.g., Fe 2 O 3 , FeO and Fe3O4 , etc. ), copper oxides (e.g., CuO and Cu2O , etc.), zinc oxide (ZnO), yttrium oxide (Y2O3), niobium oxide (Nb2O5 ) , molybdenum oxide ( MoO3 ) , indium oxide ( In2O3 , In2O ), tin oxide ( SnO2 ), tantalum oxide ( Ta2O5 ), tungsten oxide ( e.g.
  • the inorganic oxide may be an inorganic oxide that is produced by oxidizing an inorganic non-oxide over time.
  • the inorganic oxide is preferably titanium oxide, aluminum oxide or zinc oxide, more preferably aluminum oxide.
  • the first thermally conductive inorganic particles may be surface-treated.
  • the above surface treatment is different from surface modification using a surface modifier, which will be described later.
  • a functional group is introduced to the particle surface of the first thermally conductive inorganic particles, making it easier to interact with the first thermally conductive inorganic particles and the curable compound, etc., and improving the thermal conductivity of the thermally conductive sheet. It is presumed that the properties, peel strength, etc. are further improved.
  • Examples of surface treatment include plasma treatment (e.g., vacuum plasma treatment, atmospheric pressure plasma treatment, aqua plasma treatment, etc.), ultraviolet irradiation treatment, corona treatment, electron beam irradiation treatment, ozone treatment, baking treatment, flame treatment, and oxidizing agents. processing.
  • the oxidizing agent treatment may be carried out under either acidic conditions (eg, pH 6 or lower) or basic conditions (eg, pH 12 or higher).
  • the first thermally conductive layer includes a surface modifier, and the first thermally conductive inorganic particles are surface-modified first thermally conductive inorganic particles together with the surface modifier adsorbed on the surface of the first thermally conductive inorganic particles. preferably configured.
  • surface modification using a surface treatment agent means a state in which the surface treatment agent is adsorbed on at least part of the surface of the first thermally conductive inorganic particles. The form of adsorption is not particularly limited as long as it is in a bound state.
  • the surface modification includes a state in which an organic group obtained by partly desorbing the surface treatment agent is bonded to the surface of the first thermally conductive inorganic particles.
  • the bond may be any bond such as covalent bond, coordinate bond, ionic bond, hydrogen bond, van der Waals bond, and metallic bond.
  • the surface modification may be such as to form a monomolecular film on at least part of the surface.
  • a monolayer is a monolayer film formed by chemisorption of a surface treatment agent and is known as a Self-Assembled MonoLayer (SAM).
  • SAM Self-Assembled MonoLayer
  • the surface modification using the surface treatment agent may be applied to only a part of the surface of the first thermally conductive inorganic particles or to the entire surface.
  • surface-modified first thermally conductive inorganic particles are first thermally conductive inorganic particles that have been surface-modified with a surface modifier. That is, the surface-modified first thermally conductive inorganic particles are a material containing the first thermally conductive inorganic particles and the surface modifier adsorbed on the surfaces of the first thermally conductive inorganic particles.
  • the first thermally conductive inorganic particles together with the surface modifier adsorbed on the surfaces of the first thermally conductive inorganic particles can constitute the surface-modified first thermally conductive inorganic particles. preferable.
  • the first thermally conductive layer may include the first thermally conductive inorganic particles and the surface modifier by including the surface-modified first thermally conductive inorganic particles in the first thermally conductive layer.
  • Some or all of the first thermally conductive inorganic particles in the first thermally conductive layer may constitute surface-modified first thermally conductive inorganic particles together with a surface modifier.
  • some of the first thermally conductive inorganic particles are surface-modified first thermally conductive inorganic particles, and at the same time, they are not involved in the formation of the surface-modified first thermally conductive inorganic particles.
  • First thermally conductive inorganic particles may be present.
  • Part or all of the surface modifier in the first thermally conductive layer may constitute the surface-modified first thermally conductive inorganic particles together with the first thermally conductive inorganic particles.
  • part of the surface modifier in the first thermally conductive layer constitutes the surface-modified first thermally conductive inorganic particles, and at the same time, there is a surface modifier that does not participate in the formation of the surface-modified first thermally conductive inorganic particles. May be present.
  • the first thermally conductive layer is a surface-modified inorganic material in which the first thermally conductive inorganic particles constituting the surface-modified first thermally conductive inorganic particles are inorganic nitrides (preferably boron nitride or aggregated boron nitride). It preferably contains a nitride (preferably surface-modified boron nitride). Part or all of the inorganic nitride (preferably boron nitride) in the first thermally conductive layer may constitute a surface-modified inorganic nitride (preferably surface-modified boron nitride) together with a surface modifier.
  • inorganic nitride preferably boron nitride or aggregated boron nitride
  • Part or all of the inorganic nitride (preferably boron nitride) in the first thermally conductive layer may constitute a surface-modified inorganic nitride
  • the first thermally conductive layer is a surface-modified inorganic oxide (preferably a surface-modified aluminum).
  • the inorganic oxide (preferably aluminum oxide) in the first thermally conductive layer may constitute a surface-modified inorganic oxide (preferably surface-modified aluminum oxide) together with the surface modifier.
  • the surface-modified first thermally conductive inorganic particles can be formed, for example, by contacting the first thermally conductive inorganic particles with a surface modifier.
  • a surface modifier for example, in the process of forming the first thermally conductive layer described later, the first thermally conductive inorganic particles, the surface modifier, and other components constituting the composition are mixed to produce the first thermally conductive layer.
  • Surface-modified first thermally conductive inorganic particles may be formed.
  • the first thermally conductive inorganic particles and a surface modifier are mixed in advance in a solvent to prepare a mixed liquid containing the surface-modified first thermally conductive inorganic particles, and from the mixed liquid,
  • the surface-modified first thermally conductive inorganic particles may be separated by means such as filtering to obtain the separated surface-modified first thermally conductive inorganic particles.
  • the separated surface-modified first thermally conductive inorganic particles may be used to prepare a composition for forming a first thermally conductive layer, which will be described later, and the composition may be used to form the first thermally conductive layer.
  • surface modifier for example, conventionally known surface modifiers such as carboxylic acids such as long-chain alkyl fatty acids, organic phosphonic acids, organic phosphoric acid esters, and organic silane molecules (eg, silane coupling agents, etc.) can be used. Further, for example, surface modifiers described in JP-A-2009-502529, JP-A-2001-192500 and JP-A-4694929 may be used.
  • the silane coupling agent is, for example, a compound having a hydrolyzable group directly bonded to the Si atom.
  • the hydrolyzable group include alkoxy groups (preferably having 1 to 10 carbon atoms) and halogen atoms such as chlorine atoms.
  • the number of hydrolyzable groups directly bonded to Si atoms 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, and it is, for example, 10,000 or less.
  • the silane coupling agent also preferably has a reactive group.
  • the reactive groups include epoxy groups, oxetanyl groups, vinyl groups, (meth)acryl groups, styryl groups, amino groups, isocyanate groups, mercapto groups, and acid anhydride groups.
  • the number of reactive groups possessed by 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, and it is, for example, 10,000 or less.
  • Silane coupling agents include, for example, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, Methoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane, and 3-ureidopropyltriethoxysilane.
  • the silane coupling agent may be a polyfunctional silane coupling agent. Examples thereof include the X-12 series of silane coupling agents (eg, X-12-1048, X-12-1050, X-12-981S and X-12-984S, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the surface modifiers may be used singly 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 mass of the first thermally conductive layer. more preferred.
  • the content of the surface modifier is preferably 0.01 to 10% by mass, more preferably 0.10 to 5% by mass, with respect to all the first thermally conductive inorganic particles. is more preferred.
  • the mass ratio of the surface modifier to the first thermally conductive inorganic particles in the surface-modified first thermally conductive inorganic particles is preferably 0.00001 to 0.5, more preferably 0.0001 to 0.1.
  • the content of the surface-modified first thermally conductive inorganic particles is 50.0 to 80.0 with respect to the total area of the first thermally conductive layer. 0% by volume is preferred, 55.0 to 75.0% by volume is more preferred, and 60.0 to 70.0% by volume is even more preferred.
  • the first thermally conductive layer contains a surface-modified nitride (preferably surface-modified boron nitride)
  • the content of the surface-modified nitride is on the other hand, 10 to 100% by mass is preferable, 40 to 100% by mass is more preferable, and 60 to 100% by mass is even more preferable.
  • the average particle size of the first thermally conductive inorganic particles is 1.0. ⁇ 300.0 ⁇ m is preferable, 5.0 to 100.0 ⁇ m is more preferable, and 10.0 to 80.0 ⁇ m is even more preferable.
  • the average particle size of the first thermally conductive inorganic particles is preferably 0.1 to 30.0 ⁇ m, more preferably 1.0 to 15.0 ⁇ m. 0 to 10.0 ⁇ m is more preferable, and 2.0 to 7.0 ⁇ m is particularly preferable.
  • the average particle size of the first thermally conductive inorganic particles can be measured using, for example, a scanning electron microscope (SEM) or a laser diffraction particle size distribution analyzer.
  • SEM scanning electron microscope
  • a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation
  • the maximum length of the particle image obtained using a scanning electron microscope (Dmax: the maximum length at two points on the contour of the particle image) and the maximum vertical length (DV-max: two straight lines parallel to the maximum length
  • Dmax the maximum length at two points on the contour of the particle image
  • DV-max two straight lines parallel to the maximum length
  • the shortest length vertically connecting two straight lines when the image was sandwiched was measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 was taken as the grain size.
  • the particle size of 100 particles was measured by this method, and the arithmetic average value was taken as the average particle size of the particles.
  • the first thermally conductive inorganic particles preferably contain an inorganic nitride, more preferably contain boron nitride, contain boron nitride, and have an average aspect ratio of 1.0 to 1.6. It is more preferable not to contain organic particles X), and it is particularly preferable to consist only of boron nitride.
  • the first thermally conductive inorganic particles may be used singly or in combination of two or more.
  • the content of the first thermally conductive inorganic particles is preferably 50.0 to 80.0% by volume, more preferably 55.0 to 75.0% by volume, with respect to the total volume of the first thermally conductive layer. 0 to 70.0% by volume is more preferable.
  • the first thermally conductive layer may contain a curable compound.
  • a curable compound is a compound having a crosslinkable group.
  • crosslinkable groups include groups having ethylenically unsaturated bonds such as vinyl groups, (meth)allyl groups and (meth)acryloyl groups; cyclic ether groups such as epoxy groups and oxetane groups; phenolic hydroxy groups and methylol. hydroxy groups such as groups; carboxylic anhydride groups;
  • the curable compound may be, for example, a known compound that can be crosslinked by radicals, acids, bases and/or heat, and specific examples thereof include epoxy compounds, maleimide compounds, phenolic compounds and acid anhydrides.
  • the curable compound preferably contains one or more selected from the group consisting of epoxy compounds, maleimide compounds, phenol compounds and acid anhydrides, and one selected from the group consisting of epoxy compounds, maleimide compounds and phenol compounds. More preferably, it contains at least one selected from the group consisting of epoxy compounds and maleimide compounds.
  • An epoxy compound is a compound having one or more epoxy groups in one molecule.
  • An epoxy group is a group having one or more hydrogen atoms (preferably one hydrogen atom) removed from an oxirane ring. If possible, the epoxy group may further have a substituent (eg, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, etc.).
  • the number of epoxy groups possessed by the 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 epoxy compound is preferably 150 or more, more preferably 300 or more.
  • the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
  • the said molecular weight is a weight average molecular weight.
  • the weight average molecular weight is the weight average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene.
  • the epoxy group content of the epoxy compound is preferably 2.0 to 20.0 mmol/g, more preferably 5.0 to 15.0 mmol/g.
  • the said epoxy group content means the number of epoxy groups which 1g of epoxy compounds have.
  • the epoxy compound also preferably has an aromatic ring group (preferably an aromatic hydrocarbon ring group).
  • the epoxy compound may or may not exhibit liquid crystallinity. That is, the epoxy compound may be a liquid crystal compound. In other words, it may be a liquid crystal compound having an epoxy group.
  • epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and bisphenol AD type epoxy compounds, which are glycidyl ethers of bisphenol A, F, S and AD; hydrogenated bisphenol A; type epoxy compound and hydrogenated bisphenol AD type epoxy compound; phenol novolac type glycidyl ether (phenol novolac type epoxy compound), cresol novolac type glycidyl ether (cresol novolac type epoxy compound) and bisphenol A novolac type glycidyl ether; Cyclopentadiene type glycidyl ether (dicyclopentadiene type epoxy compound); dihydroxypentadiene type glycidyl ether (dihydroxypentadiene type epoxy compound); polyhydroxybenzene type glycidyl ether such as glycidyl ether of dihydroxybenzene such as resorcinol (polyhydroxy benzene-type epoxy compounds); benzenepolycar
  • Each compound described above may have a substituent.
  • an aromatic ring group, a cycloalkane ring group and/or an alkylene group contained in each of the above compounds may be substituted with a substituent other than a glycidyl ether group, a glycidyl ester group, a diglycidylamino group and/or a diglycidylaminoalkylene group. may have.
  • the content of the epoxy compound is preferably 1.0 to 90.0% by mass, more preferably 2.0 to 50.0% by mass, and 4.0 to 20.0% by mass with respect to the total mass of the first heat conductive layer. % by mass is more preferred.
  • the first heat conductive layer may contain a maleimide compound.
  • the first heat conductive layer has an interpenetrating network structure with respect to the polymer structure formed by the addition reaction of the maleimide compound with the phenol compound and/or the polymer structure formed by the above addition reaction with the other components in the composition. It is believed that forming a higher density polymer structure of the first thermally conductive layer can further enhance the thermal conductivity and heat resistance (Tg) of the thermally conductive sheet. In addition, since a denser polymer structure is formed in the first heat conductive layer, it is difficult for water to enter the heat conductive sheet, and hygroscopicity is suppressed.
  • a maleimide compound means a compound having one or more maleimide groups.
  • the maleimide compound is preferably a compound having one or two maleimide groups, and more preferably a compound having two maleimide groups (bismaleimide compound).
  • the number of maleimide groups possessed by the maleimide compound is 1 or more, preferably 1 to 100, more preferably 2 to 10, and still more preferably 2.
  • the maleimide compound may be either a high molecular weight compound or a low molecular weight compound.
  • the molecular weight of the maleimide compound is preferably from 100 to 3,000, more preferably from 200 to 2,000, even more preferably from 300 to 1,000.
  • the maleimide group possessed by the maleimide compound is preferably a group represented by formula (M).
  • X and Y each independently represent a hydrogen atom or a substituent.
  • substituents include known substituents (eg, alkyl group, etc.).
  • X and Y are preferably hydrogen atoms.
  • the maleimide compound is also preferably a compound having one or more (preferably 1 to 10) aromatic ring groups (eg, benzene ring group, etc.).
  • the maleimide compound is preferably a compound represented by Formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent.
  • an alkyl group is preferable.
  • the alkyl group may be linear or branched, and preferably has 1 to 10 carbon atoms.
  • R 1 and/or R 2 represent a substituent, it is also preferred that R 1 and/or R 2 are present at a position adjacent to the maleimide group on the benzene ring group.
  • R 1 and R 2 preferably represent different substituents, more preferably R 1 represents a methyl group and R 2 represents an ethyl group.
  • L 1 represents a divalent linking group.
  • the divalent linking group include an ether group (--O--), a carbonyl group (--CO--), an ester group (--COO--), and a thioether group (--S--).
  • R is a hydrogen atom or an alkyl group
  • divalent aliphatic hydrocarbon group e.g., alkylene group, cycloalkylene group, alkenylene group (—CH ⁇ CH— etc.), alkynylene groups (—C ⁇ C—, etc.
  • divalent aromatic ring groups arylene groups and heteroarylene groups
  • the number of carbon atoms in the divalent linking group represented by L 1 is preferably 1 or more, more preferably 1-100, even more preferably 3-15.
  • L 1 is preferably a group represented by “* p —(L 2 —Ar) k —* q ”.
  • * q represents the bonding position on the side directly bonded to the maleimide group
  • * p represents the bonding position on the opposite side.
  • k represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1.
  • L 2 represents a single bond, -C(R 3 )(R 4 )-, -O- or -CO-, preferably -C(R 3 )(R 4 )-.
  • R 3 and R 4 each independently represent a hydrogen atom or a substituent, preferably an alkyl group (which may be linear or branched and has 1 to 10 carbon atoms).
  • Ar represents an arylene group.
  • the number of ring member atoms in the arylene group is preferably 6 to 15, more preferably 6.
  • the number of substituents is preferably 1-4, more preferably 1-2.
  • an alkyl group (which may be linear or branched and has 1 to 10 carbon atoms) is preferable.
  • Structures that Ar can have include, for example, structures that can have a benzene ring group bonded to R 1 and R 2 , which are clearly shown in formula (1).
  • the plurality of L 2 and the plurality of Ar may be the same or different.
  • n 1, two groups, a maleimido group and a group represented by "-(L 1 ) m -maleimido group", on the benzene ring group bonded to R 1 and R 2 are mutually ortho It may be placed at the meta-position, it may be placed at the para-position. Among others, the above two groups are preferably arranged at the meta-position or the para-position.
  • n 1
  • the divalent linking group represented by L1 has 3 to 15 carbon atoms. preferable.
  • the content of the maleimide compound is preferably 0.1 to 40.0% by mass, more preferably 1.0 to 15.0% by mass, and 5.0 to 20.0% by mass with respect to the total mass of the first heat conductive layer. % by mass is more preferred.
  • a phenolic compound is a compound with one or more phenolic hydroxy groups.
  • the number of phenolic hydroxy groups possessed by the phenol compound is preferably 2 or more, more preferably 2-10.
  • the phenol compound preferably has a triazine skeleton. Having a triazine skeleton means that the phenol compound has one or more (preferably 1 to 5) triazine ring groups in the molecule.
  • the phenol compound is also preferably a compound represented by Formula (Z1).
  • the phenol compound preferably contains a compound represented by formula (Z1), and the phenol compound may be the compound represented by formula (Z1) itself.
  • the content of the compound represented by formula (Z1) is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and even 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, more preferably an integer of 0 to 10.
  • L represents a divalent organic group. Examples of the divalent organic group include a divalent aromatic ring group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, and a substituent divalent aliphatic cyclic groups, -O-, -S-, -N(R N )- or -CO-, and groups combining these.
  • RN represents a hydrogen atom or a substituent. Examples of substituents represented by RN include straight-chain alkyl groups and branched-chain alkyl groups having 1 to 5 carbon atoms.
  • substituents which the aromatic ring group, the aliphatic hydrocarbon group and the aliphatic ring group represented by L may have include, for example, a linear alkyl group having 1 to 5 carbon atoms and a branched A chain alkyl group is mentioned.
  • R Z represents a hydrogen atom or a substituent.
  • the substituent represented by R Z 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 alkyl having 1 to 6 carbon atoms. groups are more preferred.
  • the ratio of R Z representing a substituent among (3+r) R Zs present is preferably 30% or more, more preferably 50% or more, and even more preferably 65% or more.
  • the upper limit is preferably 90% or less, more preferably 80% or less.
  • At least one of (3+r) R 2 Zs present in the formula (Z1) (eg, 1 to 2) may represent a hydrogen atom.
  • R z preferably R z which is a substituent
  • OH in formula (Z1) the R z (preferably R z which is a substituent) is bonded to the benzene ring group It is also preferred to be in the para position to NH.
  • phenol compound other phenol compounds may be included in addition to the above.
  • Other phenolic compounds include, for example, bisphenol A, F, S, AD, benzenepolyols such as benzenediol and benzenetriol, biphenylaralkyl-type phenolic resins, phenolic novolak resins, cresol novolak resins, aromatic hydrocarbon formaldehyde resins, modified phenolic resins.
  • dicyclopentadiene phenol addition type resin dicyclopentadiene phenol addition type resin, phenol aralkyl resin, polyhydric phenol novolac resin synthesized from polyhydric hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol Phenol co-condensed novolac resins, naphthol cresol co-condensed novolac resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and alkoxy group-containing aromatic ring-modified novolac resins can be mentioned.
  • the molecular weight of the phenol compound is preferably 225-2000, more preferably 225-1000.
  • the said molecular weight is a weight average molecular weight.
  • the hydroxy 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 hydroxy group content means the number of hydroxy groups (preferably phenolic hydroxy groups) possessed by 1 g of the phenol compound.
  • the phenol compound may or may not have an active hydrogen-containing group (for example, a carboxyl group) capable of polymerizing with the epoxy compound.
  • the content of active hydrogen in the phenol compound (the total content of hydrogen atoms in hydroxy groups, carboxy groups, etc.) 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.
  • composition of the present invention may contain, in addition to the phenol compound, a compound having a group capable of reacting with an epoxy compound (hereinafter also referred to as "other active hydrogen-containing compounds").
  • a compound having a group capable of reacting with an epoxy compound hereinafter also referred to as "other active hydrogen-containing compounds”
  • the mass ratio of the content of other active hydrogen-containing compounds to the content of phenolic compounds is preferably 0 to 1, more preferably 0 to 0.1. , 0 to 0.05 are more preferred.
  • the content of the phenol compound is preferably 1.0 to 90.0% by mass, more preferably 1.0 to 50.0% by mass, and 2.0 to 30.0% by mass with respect to the total mass of the first heat conductive layer. % by mass is more preferred, and 3.0 to 10.0% by mass is particularly preferred.
  • the content of the maleimide compound is preferably 1 to 200% by mass, more preferably 5 to 100% by mass, more preferably 10 to 80% by mass, more preferably 20 to 80% by mass, based on the total content of the epoxy compound and the phenol compound. % by mass is more preferred.
  • the content of the maleimide compound is preferably 1 to 500% by mass, more preferably 20 to 300% by mass, still more preferably 50 to 200% by mass, and particularly preferably 70 to 180% by mass, relative to the content of the phenol compound. .
  • the total content of the epoxy compound and the phenol compound is preferably 3-90% by mass, more preferably 5-50% by mass, and even more preferably 7-40% by mass, relative to the total mass of the first heat conductive layer.
  • the ratio of the total number of epoxy groups contained in the epoxy compound to the number of hydroxy groups (preferably phenolic hydroxy groups) contained in the phenol compound is 3/97 to 97/3 is preferred, 30/70 to 70/30 is more preferred, 40/60 to 60/40 is even more preferred, and 45/55 to 55/45 is particularly preferred. That is, the content ratio of the phenolic compound and the epoxy compound is preferably such that the "number of epoxy groups/number of phenolic hydroxy groups" is within the above range.
  • Equivalent ratio (number of epoxy groups/activity
  • the number of hydrogen atoms) is preferably 3/97 to 97/3, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40, and particularly preferably 45/55 to 55/45.
  • the first thermally conductive layer may contain an acid anhydride.
  • An acid anhydride is a compound having one or more acid anhydride groups (groups represented by --CO--O--CO--).
  • the number of acid anhydride groups possessed by the acid anhydride is 1 or more, preferably 2 or more, and more preferably 3 or more.
  • the upper limit of the above number is, for example, 1000 or less.
  • the molecular weight of the acid anhydride (the weight average molecular weight if there is a molecular weight distribution) is preferably 100 or more, more preferably 2000 or more, and even more preferably 6000 or more.
  • the upper limit of the molecular weight is preferably 100,000 or less, more preferably 30,000 or less, and even more preferably 17,000 or less.
  • the acid anhydride may be a low-molecular-weight compound or a high-molecular-weight compound.
  • Acid anhydrides that are low-molecular-weight compounds include, for example, maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride.
  • the acid anhydride which is a polymer compound
  • the acid anhydride group may be incorporated in the main chain or may be present in the side chain.
  • the acid anhydride groups contained in the repeating units are assumed to be incorporated in the main chain.
  • a commercially available product may be used as the acid anhydride.
  • Commercially available acid anhydrides include, for example, the SMA series manufactured by Tomoe Industries (XIRAN series manufactured by Polyscope Polymers BV), the OREVAC T series manufactured by Arkema, and the Alastor series manufactured by Arakawa Chemical Industries.
  • the content of the acid anhydride is preferably 0.01-40.0% by mass, more preferably 0.1-10.0% by mass, and 0.6-5. 0% by mass is more preferred.
  • the first thermally conductive layer preferably contains a curing accelerator.
  • curing accelerators include trisorthotolylphosphine, triphenylphosphine, boron trifluoride amine complex, compounds described in paragraph [0052] of JP-A-2012-067225, tetraphenylphosphonium tetraphenylborate (TPP- K), tetraphenylphosphonium tetra-p-tolylborate (TPP-MK), tetra-n-butylphosphonium laurate (TBP-LA), bis(tetra-n-butylphosphonium) pyromellitate and bis(naphthalene- Onium salt curing accelerators such as quaternary phosphonium compounds (phosphonium salts) such as 2,3-dioxy)phenyl silicate adducts.
  • the curing accelerator preferably contains a phosphorus atom-containing compound or a phosphonium salt, more preferably a phosphorus atom-containing compound.
  • the curing accelerator may be a compound having a phosphorus atom or the phosphonium salt itself.
  • the curing accelerator contains a phosphonium salt, the storage stability of the first heat conductive layer is excellent.
  • the content of the curing accelerator is preferably 0.002% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.07% by mass or more, relative to the total mass of the first heat conductive layer.
  • the upper limit is preferably 5.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less with respect to the total mass of the first heat conductive layer.
  • the first heat conductive layer may contain resin.
  • resins include cured products of the above-described curable compounds. Specifically, one or more selected from the group consisting of an epoxy compound and a maleimide compound and a cured product of a phenol compound can be mentioned.
  • the cured product preferably has one or more selected from the group consisting of epoxy groups and maleimide groups, and phenolic hydroxy groups.
  • the total content of the curable compound and its cured product is preferably 20-50% by volume, more preferably 25-45% by volume, and even more preferably 30-40% by volume, relative to the total volume of the first heat conductive layer.
  • the first thermally conductive layer may be a layer subjected to pressure treatment.
  • the pressure treatment removes voids and the like in the first heat conductive layer, and as a result, the thermal conductivity of the heat conductive sheet after lamination is excellent.
  • the thermally conductive sheet has a second thermally conductive layer disposed on only one of the two major surfaces of the first thermally conductive layer.
  • the second thermally conductive layer includes second thermally conductive inorganic particles and a curable compound.
  • the second thermally conductive layer contains a surface modifier, and the second thermally conductive inorganic particles are surface-modified second thermally conductive inorganic particles together with the surface modifier adsorbed on the surface of the second thermally conductive inorganic particles. preferably configured. Agglomerated boron nitride is preferable as the second thermally conductive inorganic particles constituting the surface-modified second thermally conductive inorganic particles.
  • the aggregated boron nitride, the surface modifier, and the surface-modified second thermally conductive inorganic particles are aggregated boron nitride, the surface modifier, and the surface-modified first thermally conductive inorganic particles, respectively, which the first thermally conductive inorganic particles may contain.
  • the inorganic particles it is synonymous with surface-modified inorganic particles composed of second thermally conductive inorganic particles, and the preferred embodiments are also the same.
  • the second thermally conductive inorganic particles include agglomerated boron nitride and thermally conductive inorganic particles X.
  • the thermally conductive inorganic particles X have an average aspect ratio of 1.0 to 1.6 and are thermally conductive inorganic particles different from the aggregated boron nitride.
  • Thermally conductive inorganic particles that can form the thermally conductive inorganic particles X include the inorganic particles exemplified above for the first thermally conductive inorganic particles (specifically, inorganic nitrides, inorganic oxides, etc.).
  • thermally conductive inorganic particles X for example, among the first thermally conductive inorganic particles, inorganic nitrides and inorganic oxides other than aggregated boron nitride and having an average aspect ratio of 1.0 to 1.6. Certain thermally conductive inorganic particles are included. As the thermally conductive inorganic particles X, inorganic oxides having an average aspect ratio of 1.0 to 1.6 are preferable, and aluminum oxide having an average aspect ratio of 1.0 to 1.6 is more preferable.
  • the second thermally conductive inorganic particles may contain other thermally conductive inorganic particles.
  • the other thermally conductive inorganic particles are not particularly limited as long as they are other than the aggregated boron nitride and the thermally conductive inorganic particles X.
  • the average particle size of the thermally conductive inorganic particles X is often 0.1 to 300.0 ⁇ m, preferably 1.0 to 100.0 ⁇ m, more preferably 1.0 to 15.0 ⁇ m, and 2.0 to 10 ⁇ m. 0 ⁇ m is more preferred, and 2.0 to 7.0 ⁇ m is particularly preferred.
  • the average aspect ratio of the thermally conductive inorganic particles X is 1.0 to 1.6, preferably 1.0 to 1.55, more preferably 1.0 to 1.50.
  • the average aspect ratio is obtained by measuring the major axis and minor axis of any 100 inorganic particles observed with a TEM (transmission electron microscope) or SEM (scanning electron microscope), The aspect ratio (major axis/minor axis) of each inorganic particle is calculated, and the arithmetic mean of 100 aspect ratios is obtained.
  • the major diameter of the particles means the length in the major axis direction of the particles
  • the minor diameter of the particles means the length of the particles orthogonal to the major axis direction of the particles.
  • the content of the second thermally conductive inorganic particles is 40.0 to 60.0% by volume, preferably 45.0 to 55.0% by volume, and 50.0% by volume with respect to the total volume of the second thermally conductive layer. ⁇ 55.0% by volume is more preferred.
  • the content of the second thermally conductive inorganic particles is, for example, when the second thermally conductive inorganic particles consist of aggregated boron nitride and thermally conductive inorganic particles X, the aggregated boron nitride and thermally conductive inorganic particles X means the total content of
  • the content of aggregated boron nitride is preferably 25.0 to 55.0% by volume, more preferably 30.0 to 55.0% by volume, more preferably 35.0 to 50%, relative to the total volume of the second heat conductive layer. 0 vol % is more preferred.
  • the content of the thermally conductive inorganic particles X is preferably 5.0 to 30.0% by volume, more preferably 7.5 to 27.5% by volume, and 10.0% by volume with respect to the total volume of the second thermally conductive layer. ⁇ 25.0% by volume is more preferred.
  • the volume ratio of aggregated boron nitride to thermally conductive inorganic particles X is preferably 2.5 to 10.5. 2.8 to 5.0 is more preferred.
  • the curable compound is synonymous with the curable compound that the first heat conductive layer may contain, and the preferred embodiments are also the same.
  • the second heat conductive layer may contain a cured product of a curable compound. Specifically, one or more selected from the group consisting of an epoxy compound and a maleimide compound and a cured product of a phenol compound can be mentioned.
  • the cured product preferably has one or more selected from the group consisting of epoxy groups and maleimide groups, and phenolic hydroxy groups.
  • the second heat conductive layer may contain components that the first heat conductive layer may contain (for example, a curing accelerator, etc.).
  • first thermally conductive layer and second thermally conductive layer [Relationship between first thermally conductive layer and second thermally conductive layer]
  • the first thermally conductive layer and the second thermally conductive layer satisfy requirement A and requirement B.
  • the average thickness of the first thermally conductive layer is greater than the average thickness of the second thermally conductive layer.
  • the value obtained by subtracting the average thickness of the second heat conductive layer from the average thickness of the first heat conductive layer is preferably 55 to 190 ⁇ m, more preferably 65 to 170 ⁇ m, and even more preferably 75 to 150 ⁇ m.
  • the average film thickness of the first heat conductive layer is preferably 70-250 ⁇ m, more preferably 85-225 ⁇ m, even more preferably 100-200 ⁇ m, and particularly preferably 100-150 ⁇ m.
  • the average film thickness of the second heat conductive layer is preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, even more preferably 10 to 70 ⁇ m.
  • a method for measuring the average film thickness of the first thermally conductive layer and the second thermally conductive layer for example, a method of cutting out a section of the thermally conductive sheet and observing the section with an SEM for measurement can be mentioned.
  • Examples of the method for adjusting the average film thickness of the first thermally conductive layer and the second thermally conductive layer include a method of applying an arbitrary pressure after forming the amount of each layer-forming composition and forming each layer.
  • Requirement B The content of the first thermally conductive inorganic particles in the total area of the first thermally conductive layer is greater than the content of the second thermally conductive inorganic particles in the total area of the second thermally conductive layer. There is no particular limitation as long as the content of the first thermally conductive inorganic particles relative to the total volume of the first thermally conductive layer is greater than the content of the second thermally conductive inorganic particles relative to the total volume of the second thermally conductive layer.
  • the value obtained by subtracting the content of the second thermally conductive inorganic particles relative to the total area of the second thermally conductive layer from the content of the first thermally conductive inorganic particles relative to the total area of the first thermally conductive layer is 5.0 to 65.0% by volume is preferred, 8.0 to 45.0% by volume is more preferred, and 10.0 to 25.0% by volume is even more preferred.
  • the content of each thermally conductive inorganic particle in each thermally conductive layer is as described above.
  • the thermally conductive sheet may have a base material.
  • the base material is a member that supports the heat conductive sheet, and may be finally peeled off.
  • the substrate may have either a single layer structure or a multilayer structure.
  • the shape of the substrate is preferably sheet-like.
  • Substrates include, for example, plastic materials, metal materials, and glass. Examples of plastic materials include polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives, and silicones.
  • Metal materials include, for example, copper and aluminum.
  • the substrate is preferably surface-treated. Surface treatments include, for example, release treatment and roughening treatment.
  • the film thickness of the substrate is preferably 50-300 ⁇ m, more preferably 75-250 ⁇ m.
  • the heat conductive sheet is preferably insulating (electrically insulating).
  • the volume resistivity of the heat conductive sheet at 23° C. and 65% relative humidity is preferably 10 10 ⁇ cm or more, more preferably 10 12 ⁇ cm or more, and still more preferably 10 14 ⁇ cm or more.
  • the upper limit is preferably 10 18 ⁇ cm or less.
  • the thermal conductivity of the thermally conductive sheet is preferably isotropic.
  • the method for producing a thermally conductive sheet includes a first thermally conductive layer forming step of applying a composition for forming a first thermally conductive layer on a first substrate to form a first thermally conductive layer; a second thermally conductive layer forming step of applying a composition for forming a second thermally conductive layer on a second substrate to form a second thermally conductive layer; A manufacturing method including a bonding step of bonding together the surface of the first thermally conductive layer opposite to the first substrate and the surface of the second thermally conductive layer opposite to the second substrate is preferred.
  • the method for producing a thermally conductive sheet further includes a step of modifying the surface of the first thermally conductive inorganic particles or the second thermally conductive inorganic particles using a surface modifier (surface modification step). It is also preferable that the method for producing a thermally conductive sheet further includes a step of surface-treating the first thermally conductive inorganic particles or the second thermally conductive inorganic particles to obtain modified inorganic particles (modification step).
  • the modification step is preferably performed before the surface modification step. That is, it is preferable to perform the surface modification step on the surface of the modified inorganic particles. Each step will be described in detail below.
  • the modification step is a step of surface-treating the first thermally conductive inorganic particles or the second thermally conductive inorganic particles to obtain modified inorganic particles.
  • the modification step is preferably a step of bringing the first thermally conductive inorganic particles or the second thermally conductive inorganic particles into contact with an oxidizing agent in an aqueous solution to obtain modified inorganic particles.
  • the first thermally conductive inorganic particles or the second thermally conductive inorganic particles to be subjected to the modification step are as described above.
  • the above aqueous solution is preferably an alkaline aqueous solution.
  • the pH of the alkaline aqueous solution is often 8 or more, preferably 12 or more, more preferably more than 12, even more preferably 13 or more, and particularly preferably more than 13.
  • the upper limit is preferably 14 or less.
  • the pH of the aqueous solution means the pH of the aqueous solution containing the first thermally conductive inorganic particles or the second thermally conductive inorganic particles and the oxidizing agent. That is, the aqueous solution contains an alkali compound, water, the first thermally conductive inorganic particles or the second thermally conductive inorganic particles, and an oxidizing agent, if necessary.
  • the time for contacting the first thermally conductive inorganic particles or the second thermally conductive inorganic particles with the oxidizing agent in the aqueous solution is preferably 0.1 to 24 hours, more preferably 0.5 to 10 hours. .5 to 6 hours is more preferred.
  • the temperature of the aqueous solution when the first thermally conductive inorganic particles or the second thermally conductive inorganic particles and the oxidizing agent are brought into contact is preferably 1 to 95°C, more preferably 25 to 80°C, and 45 to 65°C. °C is more preferred.
  • Organic solvents include, for example, methanol, ethanol, 2-propanol, acetonitrile, cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane and tetrahydrofuran. You may use an organic solvent individually by 1 type or in 2 or more types.
  • a method of contacting the first thermally conductive inorganic particles or the second thermally conductive inorganic particles and the oxidizing agent for example, a method of contacting while stirring using a mechanical stirrer such as a three-one motor, a magnetic stirrer, or the like; For example, a solution containing an oxidizing agent is brought into contact with a cartridge filled with the first thermally conductive inorganic particles or the second thermally conductive inorganic particles while being circulated by a pump or the like.
  • the method for extracting the modified inorganic particles from the aqueous solution include a method of filtering the aqueous solution and fractionating the modified inorganic particles as filtered matter. It is also preferable to wash the removed modified inorganic particles with water and/or an organic solvent. After washing, the inorganic particles are preferably dried in an oven or the like.
  • the content of water in the aqueous solution is preferably 20 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 65 to 90% by mass, relative to the total mass of the aqueous solution.
  • oxidizing agent used in the modification step examples include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; nitrates such as cerium ammonium nitrate, sodium nitrate and ammonium nitrate; hydrogen peroxide and tert-butyl hydroperoxide.
  • transition metal compounds such as divalent copper compounds and manganese compounds; hypervalent iodine compounds such as potassium periodate and sodium periodate; quinone compounds such as benzoquinone, naphthoquinone, anthraquinone and chloranil; Salts of halogen oxoacids such as sodium hypochlorite and sodium chlorite are included.
  • the oxidizing agent preferably comprises a persulfate, more preferably a persulfate.
  • a catalyst may be used separately from the oxidant in order to assist the action of the oxidant. Examples of the catalyst include divalent iron compounds (such as FeSO4 ) and trivalent iron compounds. Note that the oxidizing agent and/or catalyst may be a hydrate.
  • the standard oxidation-reduction potential of the oxidizing agent is preferably 0.30 V or higher, more preferably 1.50 V or higher, and even more preferably 1.70 V or higher.
  • the upper limit is preferably 4.00 V or less, more preferably 2.50 V or less.
  • the above standard oxidation-reduction potential is a value based on a standard hydrogen electrode.
  • the oxidizing agents may be used singly or in combination of two or more.
  • the content of the oxidizing agent in the aqueous solution is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, and further 1 to 20 parts by mass, relative to 100 parts by mass of water in the aqueous solution. preferable.
  • the catalyst may be used singly or in combination of two or more.
  • the content of the catalyst is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, more preferably 0.1 with respect to 100 parts by mass of water in the aqueous solution. ⁇ 2 parts by mass is more preferred.
  • the aqueous solution preferably contains an alkaline compound in addition to the components described above.
  • the alkali compound include inorganic bases such as alkali metal hydroxides (eg, sodium hydroxide, etc.) and alkaline earth metal hydroxides; and organic bases.
  • the content of the alkaline compound in the aqueous solution may be an amount that appropriately adjusts the pH of the aqueous solution to a desired value. mentioned.
  • the surface modification step is a step of modifying the surface of the first thermally conductive inorganic particles or the second thermally conductive inorganic particles using a surface modifier.
  • the first thermally conductive inorganic particles or the second thermally conductive inorganic particles are preferably brought into contact with the surface modifier.
  • the method for bringing the first thermally conductive inorganic particles or the second thermally conductive inorganic particles into contact with the surface modifying agent includes the same method as in the modification step.
  • the surface modifier to be brought into contact with the first thermally conductive inorganic particles or the second thermally conductive inorganic particles is preferably a hydrolyzate or hydrolyzed condensate of the surface modifier. That is, the surface modifier is preferably hydrolyzed before being brought into contact with the first thermally conductive inorganic particles or the second thermally conductive inorganic particles.
  • Hydrolysis treatment is treatment for hydrolyzing the surface modifier.
  • the surface modifier is a silane coupling agent
  • the hydrolysis treatment hydrolyzes the alkoxysilyl groups of the silane coupling agent to generate silanol groups, and the silanol groups form the first thermally conductive inorganic particles or the second thermally conductive particles. It can form a bond with the surface of the conductive inorganic particles.
  • the hydrolysis method is not particularly limited as long as the conditions are such that the surface modifier is hydrolyzed. Specifically, it is preferable to use an acidic solution (eg, aqueous hydrochloric acid and acetic acid solution).
  • the acidic solution may contain an organic solvent.
  • the first base material and the second base material are synonymous with the above base material, and the preferred embodiments are also the same.
  • the first substrate and the second substrate may be the same or different.
  • the composition for forming the first thermally conductive layer and the composition for forming the second thermally conductive layer will be described in detail later.
  • composition examples include known methods. Specific examples include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and a die coating method (slit coating method).
  • the obtained coating film may be subjected to a drying treatment, if necessary.
  • Heat treatment is preferable as the drying treatment.
  • the temperature of the heat treatment is preferably a temperature at which the curing reaction of the curable compound hardly progresses, more preferably 50 to 130°C.
  • the obtained coating film may be semi-cured by subjecting it to a semi-cured state. That is, the first thermally conductive layer and the second thermally conductive layer may be semi-cured films.
  • the first thermally conductive layer is preferably a layer subjected to a semi-curing treatment in terms of excellent thermal conductivity of the thermally conductive sheet after lamination.
  • the semi-curing treatment includes heat treatment, and the heating condition is preferably a temperature at which curing of the curable compound proceeds or higher.
  • the first heat conductive layer is a layer subjected to pressure treatment (for example, pressing treatment). The pressure treatment reduces voids in the first thermally conductive layer, resulting in excellent thermal conductivity of the thermally conductive sheet after lamination.
  • Semi-curing treatment and pressure treatment may be performed separately or simultaneously.
  • the coating film on the substrate may be heated as it is without pressure to obtain a semi-cured product in a semi-cured state, or press processing may be performed.
  • a semi-cured product may be obtained by heating the coating film on the base material while using them together.
  • the press working may be performed before or after the semi-hardening treatment, or may be performed during the heating or the like. If pressing is performed in the semi-curing treatment, it may be easier to adjust the thickness of the resulting semi-cured product and/or reduce the amount of voids in the semi-cured product.
  • a press used for pressing for example, a flat plate press or a roll press may be used.
  • 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 facing each other, and the pair of rolls is rotated. It is preferable to apply pressure in the film thickness direction of the substrate with the coating film while allowing the substrate with the coating film to pass through.
  • the base material with the coating film may have the base material on only one side of the coating film, or may have the base material on both sides of the coating film.
  • the coated substrate may be passed through the roll press only once or may be passed multiple times. At the time of hardening treatment such as the semi-hardening treatment and/or the main hardening treatment, either one or both of flat press treatment and roll press treatment may be performed.
  • the lamination step for example, a method in which the surface of the first thermally conductive layer opposite to the first substrate and the surface of the second thermally conductive layer opposite to the second substrate are brought into contact with each other and pressed together.
  • the press-bonding method for example, a method of pressurizing and heating by lamination, rolls, or the like is preferable. Specifically, press working used in the above-described hardening treatment is exemplified.
  • the method for manufacturing the heat conductive sheet may further include a first heat conductive layer forming step, a second heat conductive layer forming step and/or a lamination step. That is, it may be a thermally conductive sheet having one or more first thermally conductive layers and one or more second thermally conductive layers.
  • Another method for producing a thermally conductive sheet includes a step of applying a composition for forming a first thermally conductive layer onto a first substrate to form a first thermally conductive layer; Also preferred is a manufacturing method comprising the step of further applying a composition for forming a second heat conductive layer on the first heat conductive layer to form a second heat conductive layer.
  • a manufacturing method comprising the step of further applying a composition for forming a second heat conductive layer on the first heat conductive layer to form a second heat conductive layer.
  • compositions (the composition for forming the first thermally conductive layer and the composition for forming the second thermally conductive layer) contain components contained in each thermally conductive layer and a solvent.
  • the composition for forming the first thermally conductive layer is a composition for forming the first thermally conductive layer, and contains at least the first thermally conductive inorganic particles described above.
  • the composition for forming the first thermally conductive layer may contain components other than the first thermally conductive inorganic particles (for example, a curable compound, etc.).
  • the composition for forming the second thermally conductive layer is a composition for forming the second thermally conductive layer, and contains at least the second thermally conductive inorganic particles and the curable compound described above.
  • the composition for forming the second thermally conductive layer may contain components other than the second thermally conductive inorganic particles and the curable compound.
  • the composition preferably contains a solvent.
  • Organic solvents are preferred as solvents.
  • Organic solvents include, for example, cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane and tetrahydrofuran.
  • the content of the solvent is preferably an amount that makes the solid content concentration of the composition 20 to 90% by mass, more preferably 30 to 85% by mass, and 50 to 80% by mass. is more preferable.
  • the "solid content" of the composition means the components forming each thermally conductive layer formed using the composition, and when the composition contains a solvent, it means all components excluding the solvent.
  • a liquid component is also considered as a solid content.
  • the solvent content is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, even more preferably 20 to 50% by mass, relative to the total mass of the composition.
  • Methods for producing the composition include, for example, known methods.
  • Examples of the method for producing the composition include a method for mixing components contained in each heat conductive layer with a solvent. When mixing, each component may be mixed all at once or sequentially.
  • a method for mixing the components for example, a known method can be used.
  • the mixing device used for mixing is preferably a submerged disperser. A homogenizer is mentioned. You may use a mixing apparatus individually by 1 type or in 2 or more types. Degassing may be performed before, after and/or simultaneously with mixing.
  • the thermally conductive sheet of the present invention can be used, for example, as a heat dissipation material, and can be used for heat dissipation of various devices.
  • a device with a heat conductive sheet is produced by arranging a heat conductive sheet on the device, and heat generated from the device can be efficiently dissipated through the heat conductive layer of the heat conductive sheet.
  • the heat conductive sheet of the present invention has excellent adhesion to the device even when laminated at low pressure, so that the heat conductive sheet can be placed on the device at low pressure, and the risk of damage to the device can be reduced.
  • the thermally conductive layer may be a thermally conductive layer containing a thermally conductive multilayer sheet to be described later.
  • the heat conductive sheet of the present invention is suitable for heat dissipation of power semiconductor devices used in electrical equipment such as personal computers, general household appliances and automobiles.
  • a semiconductor module is one of the preferred uses of the heat conductive sheet of the present invention.
  • One preferred embodiment of a semiconductor module containing the heat conductive sheet of the present invention is the embodiment shown in FIG.
  • the semiconductor module 100A is a so-called case-type semiconductor module, and includes a heat sink 30, a metal layer 32, the thermally conductive sheet 10 of the present invention, two devices 34, and a region in which the devices 34 are mounted. and a sealing material 38 disposed within the case frame 36 .
  • a conductive paste layer may be disposed between the heat sink 30 and the metal layer 32 .
  • the second heat conductive layer 14 in the heat conductive sheet 10 is arranged on the device 34 side.
  • the configuration of the device 34 is not particularly limited, it preferably includes a semiconductor chip, and more preferably has a configuration in which a circuit section, a conductive paste layer, and a semiconductor chip are laminated from the heat conductive sheet 10 side.
  • two devices 34 are shown in the semiconductor module 100A, the number is not particularly limited, and an optimum number is selected according to various uses.
  • electrical connection to the device 34 may be made using metal electrodes or wire bonds (not shown).
  • Examples of the sealing material 38 include silicone gel.
  • the heat generated in the device 34 is transferred to the heat sink 30 through the heat conductive sheet 10 and radiated outside the semiconductor module 100A system.
  • the semiconductor module 100B is a so-called molded semiconductor module, and includes a heat sink 30, a metal layer 32, the thermally conductive sheet 10 of the present invention, two devices 34, and a sealing resin 40 that seals the devices 34. .
  • the semiconductor module 100B which is a mold-type semiconductor module, can fix and seal the device 34 more firmly than the semiconductor module 100A, which is a case-type semiconductor module.
  • the method of manufacturing the semiconductor module 100B is not particularly limited.
  • a method of manufacturing a semiconductor module by forming a sealing resin 40 in a mold, and placing a laminate having a configuration other than the sealing material 40 of the semiconductor module 100B in a mold, pouring the mold resin there, and applying heat.
  • a conductive paste layer may be disposed between the heat sink 30 and the metal layer 32 .
  • two devices 34 are shown in the semiconductor module 100B, the number is not particularly limited, and an optimum number is selected according to various uses. Also, electrical connection to the device 34 may be made using metal electrodes or wire bonds (not shown).
  • the sealing resin 40 for example, a resin obtained by thermosetting an epoxy resin can be used.
  • the heat generated in the device 34 is transferred to the heat sink 30 through the heat conductive sheet 10 and radiated outside the system of the semiconductor module 100B.
  • the metal layer 32 is arranged between the heat sink 30 and the heat conductive sheet 10, but the metal layer 32 is not arranged as in the semiconductor module 100C shown in FIG. It doesn't have to be.
  • a conductive paste layer may be arranged between the heat sink 30 and the thermally conductive sheet 10 in the semiconductor module 100C.
  • two semiconductor modules may be arranged so as to face each other.
  • laminates including a heat sink 30, a metal layer 32, the thermally conductive sheet 10 of the present invention, and a device 34 are arranged to face each other, and the device 34 in these two laminates is arranged to face each other.
  • a sealing resin 40 is arranged between the two laminates so as to seal the . In such a mode, heat is dissipated from both sides of the semiconductor module 100D.
  • the semiconductor module 100E includes a device 34, a heat-conducting sheet 10 arranged on one side of the device 34, a metal layer 32, a heat sink 30, and a heat-conducting sheet 100 arranged on the other side of the device 34. It includes a sheet 10 , a metal layer 32 , a heat sink 30 and an encapsulating resin 40 encapsulating the device 34 .
  • the heat generated in the device 34 is transferred to the two heat sinks 30 via the heat conductive sheets 10 arranged on both sides of the device 34, and is radiated outside the semiconductor module 100E system. ing.
  • the agglomerated boron nitride in the NaOH water was collected by filtration, and the filtered agglomerated boron nitride was washed with water (500 mL) and acetonitrile (250 mL) to form a denatured agglomerate. Boron nitride 1 was obtained.
  • the resulting modified aggregated boron nitride 1 was stirred in acetonitrile (100 mL), and a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.: X12-984S) hydrolysis adjustment solution (1.25 g) was further added to the acetonitrile. added.
  • the acetonitrile was stirred at room temperature for 3 hours to carry out adsorption treatment (adsorption step). After filtering the modified aggregated boron nitride 1 in the acetonitrile, the filtered modified aggregated boron nitride 1 was washed with acetonitrile (100 mL) and dried in an oven at 40 ° C., thereby surface-modified aggregated boron nitride. Boron was obtained.
  • the silane coupling agent hydrolysis adjustment solution is prepared by mixing silane coupling agent (1 g), ethanol (500 ⁇ L), 2-propanol (500 ⁇ L), water (720 ⁇ L) and acetic acid (100 ⁇ L) and stirring for 1 hour.
  • X12-984S is a polymer-type silane coupling agent having an epoxy group and an ethoxysilyl group.
  • NaOH water NaOH: 40 g/water: 400 ml
  • aggregated boron nitride HP40MF100, 50 g
  • sodium persulfate water sodium persulfate: 9.6 g/water: 100 ml
  • the pH of the liquid was 14.
  • the content of the surface modifier in the surface-modified BN was more than 0% by mass and less than 1% by mass with respect to the total mass of the surface-modified BN.
  • TPP-MK Tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokko Chemical Industry Co., Ltd.)
  • composition for forming a first thermally conductive layer and a composition for forming a second thermally conductive layer were prepared in the following procedure. Specifically, first, an epoxy compound and a phenol compound were blended in equivalent amounts (an amount that equalizes the number of epoxy groups in the epoxy compound and the number of hydroxy groups in the phenol compound) to prepare a mixture. After mixing the above mixture and solvent, an acid anhydride, a curing accelerator and a maleimide compound were mixed. After that, each thermally conductive inorganic particle was further added.
  • compositions curable compositions
  • Tables 1 and 2 the content (% by mass) of each component with respect to the total mass of the composition for forming the first thermally conductive layer or the composition for forming the second thermally conductive layer is shown.
  • “remainder” means that the amount of solvent was adjusted so that the total amount with other components was 100% by mass.
  • each composition for forming the first heat conductive layer was uniformly applied onto the release surface of a release-treated PET film (PET756501, manufactured by Lintec, film thickness 75 ⁇ m) with a clearance of 450 ⁇ m. , and dried at 50° C. for 4 minutes to obtain a first laminate having a first thermally conductive layer with a film thickness of 220 ⁇ m.
  • the obtained first laminate was further dried at 120° C. for 5 minutes, and then cut into 5 cm ⁇ 5 cm.
  • the resulting cut material was vacuum-pressurized at a temperature of 188° C. and a pressure of 20 MPa.
  • each composition for forming the second heat conductive layer was uniformly applied with a clearance of 60 ⁇ m onto the release surface of a release-treated PET film (PET756501, Lintec, film thickness: 75 ⁇ m). It was applied and dried at 50° C. for 2 minutes to obtain a second laminate having a second heat conductive layer with a film thickness of 53 ⁇ m. The obtained second laminate was further dried at 120° C. for 2 minutes, and then cut into 5 cm ⁇ 5 cm.
  • the surface of the second heat conductive layer opposite to the PET film of the second laminate having the second heat conductive layer is replaced with the first heat conductive layer opposite to the PET film of the first heat conductive layer having the first heat conductive layer. It was attached to the surface of the thermally conductive layer and vacuum-pressurized at a temperature of 188° C. and a pressure of 5 MPa to obtain a resin sheet.
  • the PET films on both sides of the obtained resin sheet were peeled off to obtain the thermally conductive sheets of each example and each comparative example.
  • the thickness of the first thermally conductive layer of the obtained thermally conductive sheet was 120 ⁇ m
  • the thickness of the second thermally conductive layer of the obtained thermally conductive sheet was 36 ⁇ m.
  • the obtained thermal diffusivity was multiplied by the specific gravity and the specific heat to calculate the thermal conductivity in the film thickness direction of the sample for thermal conductivity measurement.
  • the thermal conductivity of the samples for thermal conductivity measurement was classified according to the following criteria, and the thermal conductivity was evaluated.
  • each composition for forming the first heat conductive layer was uniformly applied onto the release surface of a release-treated PET film (PET756501, manufactured by Lintec, film thickness 75 ⁇ m) with a clearance of 450 ⁇ m, After drying at 50° C. for 4 minutes, a laminate having a first heat conductive layer with a film thickness of 220 ⁇ m was obtained. The obtained laminate was further dried at 120° C. for 5 minutes, and then cut into 5 cm ⁇ 5 cm.
  • each composition for forming the second heat conductive layer was uniformly applied with a clearance of 48 ⁇ m and dried at 50° C. for 3 minutes to obtain a second laminate having a second heat conductive layer with a thickness of 37 ⁇ m.
  • the release-treated PET film of the first laminate was peeled off, and the exposed first thermally conductive layer and the exposed second thermally conductive layer of the second laminate were directly combined and subjected to vacuum heating at a temperature of 188 ° C. and a pressure of 5 MPa.
  • the thickness of the first heat conductive layer of the obtained laminate 3 was 120 ⁇ m, and the thickness of the second heat conductive layer of the obtained heat conductive sheet for adhesion evaluation was 36 ⁇ m. Furthermore, the laminate 3 was cut into a size of 2.0 cm width ⁇ 5.0 cm length and a size of 0.5 cm width ⁇ 5.0 cm length.
  • the copper foil peel strength of each laminate 3 obtained above was measured using a digital force gauge (ZTS-200N, manufactured by Imada) and a 90-degree peel test jig (P90-200N-BB, manufactured by Imada) according to JIS. It was measured according to the method for measuring peel strength in the state described in C 6481.
  • the peeling of the copper foil in the peel strength test was performed at an angle of 90° with respect to the laminate 3 at a peeling speed of 50 mm/min.
  • Insulation reliability measurement under high temperature and high humidity conditions and insulation reliability measurement under high temperature and high humidity conditions were carried out as insulation evaluation.
  • ⁇ Dielectric breakdown voltage measurement> A sample for dielectric breakdown voltage measurement was prepared in the same manner as the sample for insulation reliability measurement. Using "YST-243-100RHO" manufactured by Yamayo Test Instruments Co., Ltd., apply 1 kV to the dielectric breakdown voltage measurement sample in oil at 25 ° C. and 175 ° C. If it does not break for 20 seconds, the applied voltage is The measurement was repeated by increasing the voltage by 0.5 V and evaluating for 20 seconds. The maximum voltage at which no breakdown occurred was defined as the dielectric breakdown voltage, and the dielectric breakdown voltage property was evaluated by classifying the samples according to the following criteria. A: 5 kV or more B: 2 kV or more and less than 5 kV C: less than 2 kV
  • the thermally conductive sheet of the present invention has excellent thermal conductivity and adhesion. It was confirmed that the effect of the present invention is more excellent when the content of the second thermally conductive inorganic particles is 45.0 to 55.0% by volume with respect to the total volume of the second thermally conductive layer (implementation (comparison with Examples 1 to 5, etc.). It was confirmed that the effect of the present invention is more excellent when the volume ratio of the aggregated boron nitride to the thermally conductive inorganic particles X in the second thermally conductive layer is 2.8 to 5.0 (Example 1 , 6-10, etc.).
  • At least one of the first thermally conductive layer and the second thermally conductive layer further comprises a surface modifier, and the aggregated boron nitride is surface-modified aggregated nitriding with the surface modifier adsorbed on the surface of the aggregated boron nitride.
  • boron is composed (using the surface-modified first thermally conductive inorganic particles and/or the surface-modified first thermally conductive inorganic particles), the thermal conductivity, adhesion, insulation and void generation suppression are improved. It was confirmed to be excellent (comparison with Examples 3, 11, 15 and 16, etc.).
  • thermally conductive sheet 12 first thermally conductive layer 14 second thermally conductive layer 16 first thermally conductive inorganic particles 18 second thermally conductive inorganic particles 20 agglomerated boron nitride 22 thermally conductive inorganic particles X 30 heat sink 32 metal layer 34 device 36 case frame 38 sealing material 40 sealing resin 100A, 100B, 100C, 100D, 100E semiconductor module

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