JP6606410B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate using a metal body and an insulating material.

  In recent years, miniaturization and high performance of electric devices have been advanced. Along with this, the mounting density of electronic components is increasing, and the need to dissipate heat generated from electronic components is increasing. In order to dissipate heat, a heat conductive composition containing a heat conductive filler is used.

  In the following Patent Document 1, (A) binder resin, (B1) boron nitride powder 15 to 70% by weight, (B2) ceramic powder (excluding boron nitride powder) 5 to 50% by weight, (B3) A thermally conductive resin composition containing 5 to 30% by weight of a porous moisture absorbent (excluding an alkaline earth metal oxide) is disclosed. Patent Document 1 discloses a thermally conductive film sheet having at least one thermally conductive resin layer formed from the thermally conductive resin composition.

The following Patent Document 2 discloses an insulating resin sheet used for a heat radiation fin integrated power module. The power circuit portion and the heat radiating fin are electrically insulated by the insulating resin sheet. As this insulating resin sheet, a bisphenol A type epoxy resin containing 71.3 wt% of alumina filler (α-Al ₂ O ₃ ) is used.

  Patent Document 3 below discloses a thermally conductive sheet in which some or all of boron nitride particles are aggregated particles and dispersed in a thermosetting resin. This heat conductive sheet further contains metal oxide particles. The metal oxide particles and the boron nitride particles are contained in a total of 40% by volume to 70% by volume. The volume ratio of the metal oxide particles to the boron nitride particles is 10:90 to 50:50. The median diameter of the metal oxide particles is 0.5 μm to 30 μm.

  Patent Document 4 below discloses a thermally conductive sheet containing scaly boron nitride having an average major axis of 3 μm or more and 50 μm or less in a matrix resin in a proportion of 30% by volume to 80% by volume. Patent Document 4 discloses a power module including a heat conductive sheet. A ten-point average height of 1/3 or more of the average major axis of the scaly boron nitride and 1/2 or less of the thickness of the thermal conductive sheet on the surface of the member in contact with the thermal conductive sheet on the thermal conductive sheet side. Concavities and convexities having a thickness Rz are formed. Patent Document 4 discloses that a power module having excellent heat dissipation characteristics can be obtained by orienting so that the major axis direction of scaly boron nitride substantially coincides with the sheet thickness direction and improving the thermal conductivity in the sheet thickness direction. Is described.

JP 2011-001452 A Japanese Patent Laid-Open No. 11-204700 JP 2013-32496 A Japanese Patent Laid-Open No. 11-60216

  The sheets as described in Patent Documents 1 to 3 are bonded to the adherend by a thermocompression process. In many cases, the bonding surface of the member to be bonded has minute irregularities. When a conventional sheet is thermocompression-bonded to a member to be bonded having such minute unevenness on the bonding surface, the resin component enters the recess and the amount of filler tends to decrease at the bonding interface. As a result, the thermal resistance on the surface of the adherend member increases, and sufficient heat dissipation may not be obtained.

  In Patent Documents 1 to 4, it is difficult not only to make the heat dissipation sufficiently high, but also to make the insulation sufficiently high.

  Furthermore, in patent document 4, although it aligns so that the major axis direction of scaly boron nitride may correspond with a sheet | seat thickness direction substantially, it is controlling the compounding property of the scaly boron nitride contained in a heat conductive sheet sufficiently. Have difficulty. As a result, the heat dissipation is not likely to be sufficiently high.

  The objective of this invention is providing the laminated body which can make high heat dissipation, high mechanical strength, and a high dielectric breakdown characteristic compatible.

  In a wide aspect of the present invention, the metal composite includes an insulating material portion, and the metal composite includes a metal body and a plurality of boron nitride nanotubes disposed on a surface of the metal body, On the surface of the insulating material portion, the metal composite is disposed from the boron nitride nanotube side, and the insulating material portion is a cured portion of a thermosetting component including a thermosetting compound and a thermosetting agent, A laminate comprising an insulating filler that is not a nanotube is provided.

  On the specific situation with the laminated body which concerns on this invention, the said boron nitride nanotube is in contact with the surface of the said metal body in the one end side of the length direction of the said boron nitride nanotube.

  In a specific aspect of the laminate according to the present invention, a ratio of a total volume of the boron nitride nanotubes in the metal composite to a total volume of the insulating filler in the insulating material portion is 0.02 or more. 0 or less.

  On the specific situation with the laminated body which concerns on this invention, the said hardened | cured material part in the said insulating material part has entered between the said some boron nitride nanotubes in the said metal composite.

  On the specific situation with the laminated body which concerns on this invention, the average diameter of the said boron nitride nanotube is 2 nm or more and 300 nm or less, and the average length of the said boron nitride nanotube is 1 micrometer or more and 200 micrometers or less.

  On the specific situation with the laminated body which concerns on this invention, the said insulating-material part contains a boron nitride nanotube.

  The laminate according to the present invention includes a metal composite and an insulating material part, and the metal composite includes a metal body and a plurality of boron nitride nanotubes disposed on a surface of the metal body, The metal composite is disposed on the surface of the insulating material portion from the boron nitride nanotube side, and the insulating material portion includes a cured portion of a thermosetting component including a thermosetting compound and a thermosetting agent. Since an insulating filler that is not a nanotube is included, it is possible to achieve both high heat dissipation, high mechanical strength, and high dielectric breakdown characteristics.

FIG. 1 is a cross-sectional view schematically showing a laminate according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The laminate according to the present invention includes a metal composite and an insulating material part. In the laminate according to the present invention, the metal composite includes a metal body and a plurality of (C) boron nitride nanotubes (Boron Nitride Nanotube or BNNT, or BNNT (C)) disposed on the surface of the metal body. There is a thing to do. In the laminate according to the present invention, the metal composite is disposed on the surface of the insulating material portion from the (C) boron nitride nanotube side. In the laminate according to the present invention, the insulating material part is described as (A) a cured part of a thermosetting component including a thermosetting compound and (B) a thermosetting agent, and (D) a nanotube (NT). Insulative filler (which may be simply referred to as (D) insulating filler). The insulating material part is a hardened layer.

  In this invention, since said structure is provided, high heat dissipation, high mechanical strength, and a high dielectric breakdown characteristic can be made compatible. Since (C) boron nitride nanotubes are arranged on the surface of the metal body, the heat dissipation can be considerably improved. In addition, since (C) boron nitride nanotubes exist at the bonding interface between the metal body and the insulating material portion, the thermal resistance on the surface of the metal body is lowered. Furthermore, since the arrangement on the surface of the metal body is (C) boron nitride nanotubes, the insulation is higher than when the arrangement is carbon nanotubes (CNT) or the like. The insulating material part may be a sheet-like cured product sheet. The metal body may be a substrate or a part of the substrate.

  In the present invention, the mechanical strength of the insulating material portion can also be increased. (C) Boron nitride nanotubes contribute to the improvement of mechanical strength.

  FIG. 1 is a cross-sectional view schematically showing a laminate according to an embodiment of the present invention.

  The laminated body 1 shown in FIG. 1 includes a cured product sheet 2 (insulating material part), a first metal composite 3, and a second metal composite 4.

  Hardened material sheet 2 includes hardened material portion 11, boron nitride nanotube 12, and insulating filler 13. The insulating filler 13 is not a nanotube. The hardened | cured material part 11 is a part which the thermosetting component containing a thermosetting compound and a thermosetting agent hardened | cured, and is obtained by hardening a thermosetting component.

  The first metal composite 3 has a first metal body 21 and a plurality of boron nitride nanotubes 22 arranged on the surface of the first metal body 21. In the laminated body 1, the first metal composite 3 is disposed on the first surface of the cured product sheet 2 from the boron nitride nanotube 22 side.

  The second metal composite 4 has a second metal body 31 and a plurality of boron nitride nanotubes 32 arranged on the surface of the second metal body 31. In the laminated body 1, the second metal composite 4 is disposed from the boron nitride nanotube 32 side on the second surface opposite to the first surface of the cured product sheet 2.

  Instead of the second metal composite 4, a second metal body 31 may be used. That is, the second metal body may be disposed on the second surface of the cured product sheet 2 without using the boron nitride nanotubes.

  From the viewpoint of effectively increasing heat dissipation and mechanical strength, in the metal composite, (C) boron nitride nanotubes are placed on the surface of the metal body on one end side in the length direction of (C) boron nitride nanotubes. It is preferable to contact. From the viewpoint of effectively increasing heat dissipation, insulation, and mechanical strength, it is preferable that the other end in the length direction of the (C) boron nitride nanotube extends outward from the surface of the metal body.

  In the metal composite, the boron nitride nanotubes are preferably arranged on the surface of the metal body in a straight line from the surface of the metal body to the outside in the entire boron nitride nanotube. Since the boron nitride nanotubes are arranged in the vertical direction from the metal body, heat can be efficiently propagated in the vertical direction through the boron nitride nanotubes, so that heat dissipation is improved. At the same time, since the boron nitride nanotubes are arranged vertically from the metal body, the cured product portion of the cured product sheet can be effectively inserted between the boron nitride nanotubes. Increases adhesiveness and mechanical strength.

  Examples of the method for arranging boron nitride nanotubes on the surface of the metal body include a method for vertically orienting boron nitride nanotubes mechanically or by a magnetic field, and a method for vertically synthesizing boron nitride nanotubes. From the viewpoint of allowing the boron nitride nanotube to adhere to the surface of the metal body at one end side in the length direction of the boron nitride nanotube, a method of directly synthesizing and growing the boron nitride nanotube directly on the metal body is preferable. Examples of a method for synthesizing boron nitride nanotubes directly on a metal body include a chemical vapor deposition (CVD) method.

  From the viewpoint of effectively increasing heat dissipation, insulation and mechanical strength, the ratio of the total volume of (C) boron nitride nanotubes in the metal composite to the total volume of (D) insulating filler in the cured sheet Is preferably 0.02 or more, more preferably 0.2 or more, preferably 2.0 or less, more preferably 1.0 or less.

  From the viewpoint of effectively increasing the insulation and mechanical strength, it is preferable that the cured product portion of the cured product sheet penetrates between the plurality of boron nitride nanotubes in the metal composite.

  From the viewpoint of effectively increasing heat dissipation, insulation, and mechanical strength, the surface area portion (coverage) covered with the boron nitride nanotubes is preferably 20% in the surface area of 100% of the first metal body. Above, more preferably 30% or more, preferably 90% or less, more preferably 80% or less. From the viewpoint of effectively increasing heat dissipation, insulation, and mechanical strength, the surface area portion covered with the boron nitride nanotubes is preferably 20% or more, more preferably 100% of the surface area of the second metal body. Is 30% or more, preferably 90% or less, more preferably 80% or less. Moreover, the method of coating a desired area with boron nitride nanotubes can be adjusted by, for example, the density of the metal catalyst used when synthesizing by the CVD method, the number of coating treatments, and the like.

  The ratio of the surface area covered with the boron nitride nanotubes can be evaluated with a scanning electron microscope SEM-EDS with energy dispersive X-ray analysis. That is, the elemental analysis is performed in the cross-sectional observation of the metal body, the portion covered with the boron nitride nanotube is identified, and the coating ratio can be calculated from the total area ratio.

  The cured sheet is a cured product of a thermosetting material, and is obtained by curing the thermosetting material. The thermosetting material may be a thermosetting paste or a thermosetting sheet. The thermosetting material is preferably a thermosetting sheet. From the viewpoint of effectively increasing heat dissipation and mechanical strength, the cured product sheet and the thermosetting material according to the present invention preferably contain (C ′) boron nitride nanotubes. In order to distinguish from the (C) boron nitride nanotube in the metal composite, in the cured sheet and the thermosetting material, it is referred to as (C ′) boron nitride nanotube (or (C ′) BNNT).

  The said laminated body can be used for various uses as which heat dissipation, mechanical strength, etc. are calculated | required. The laminate is used, for example, in an electronic device such that a cured product sheet is disposed between a heat generating component and a heat radiating component.

  The material of the metal body in the first metal composite is preferably copper or aluminum. However, other materials may be used, and the material of the first metal composite is not limited. The material of the metal body in the second metal composite is preferably copper or aluminum. However, other materials may be used, and the material of the second metal composite is not limited.

((C) Boron nitride nanotubes and (C ′) Boron nitride nanotubes)
(C) Boron nitride nanotubes and (C ′) boron nitride nanotubes are nanotubes. The material of (C) boron nitride nanotube and (C ′) boron nitride nanotube is boron nitride. The shape of (C) boron nitride nanotube and (C ′) boron nitride nanotube is a tube shape. The ideal shape is a shape in which a hexagonal mesh surface forms a tube parallel to the tube axis and is a single tube or multiple tubes.

  From the viewpoint of effectively increasing heat dissipation, insulation and mechanical strength, the average diameter of (C) boron nitride nanotubes and (C ′) boron nitride nanotubes is preferably 2 nm or more, more preferably 6 nm or more, and still more preferably. It is 10 nm or more, particularly preferably 30 nm or more, preferably 300 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 50 nm or less.

  The average diameter indicates an average outer diameter in the case of a single pipe, and means the average outer diameter of the outermost pipe in the case of a multiple pipe.

  From the viewpoint of effectively increasing heat dissipation, insulation, and mechanical strength, the average length of (C) boron nitride nanotubes and (C ′) boron nitride nanotubes is preferably 1 μm or more, preferably 200 μm or less, more preferably Is 150 μm or less, more preferably 100 μm or less, and particularly preferably 80 μm or less.

  The diameters and lengths of (C) boron nitride nanotubes and (C ′) boron nitride nanotubes can be changed as appropriate by changing the synthesis method, the temperature and time during synthesis, and the like. For example, a small diameter nanotube can be obtained by the arc discharge method, and a large diameter nanotube can be obtained by the chemical vapor deposition method.

  The aspect ratio of (C) boron nitride nanotube and (C ′) boron nitride nanotube is preferably 3 or more. The upper limit of the aspect ratio of (C) boron nitride nanotube and (C ′) boron nitride nanotube is not particularly limited. The aspect ratio of (C) boron nitride nanotubes and (C ′) boron nitride nanotubes may be 100,000 or less.

  From the viewpoint of effectively increasing heat dissipation, insulation, and mechanical strength, the ratio of the average length of (C) boron nitride nanotubes to the average particle diameter of (D) insulating filler is preferably 0.01 or more. More preferably, it is 0.2 or more, preferably 200 or less, more preferably 100 or less. From the viewpoint of effectively increasing heat dissipation and mechanical strength, the ratio of the average length of (C ′) boron nitride nanotubes to the average particle diameter of (D) insulating filler is preferably 0.01 or more, more Preferably it is 0.2 or more, preferably 200 or less, more preferably 100 or less.

  The average diameter, the average length, and the aspect ratio can be obtained from observation with an electron microscope. For example, it is possible to measure with a TEM (Transmission Electron Microscope), and directly measure the diameter and length of (C) boron nitride nanotubes and (C ′) boron nitride nanotubes from the obtained images. The forms of (C) boron nitride nanotubes and (C ′) boron nitride nanotubes in the thermosetting material can be grasped by, for example, TEM (transmission electron microscope) measurement of a fiber cross section cut parallel to the axis. The average diameter, the average length, and the aspect ratio are preferably determined by an arithmetic average of 50 arbitrary images in an electron microscope image.

  (C) Boron nitride nanotubes and (C ′) boron nitride nanotubes can be synthesized using an arc discharge method, a laser heating method, a chemical vapor deposition method, or the like. A method of synthesizing borazine as a raw material using nickel boride as a catalyst is also known. Also known is a method of synthesizing boron oxide and nitrogen by using carbon nanotubes as a template. (C) Boron nitride nanotubes and (C ′) boron nitride nanotubes are not limited to those obtained by these synthesis methods. The (C) boron nitride nanotubes and (C ′) boron nitride nanotubes may be strongly acid treated or chemically modified boron nitride nanotubes.

  Among the components contained in the thermosetting material, the content of (C ′) boron nitride nanotubes is preferably 0.5% by volume or more, more preferably in 100% by volume of the components excluding the solvent and in 100% by volume of the cured product. Is 5% by volume or more, preferably 40% by volume or less, more preferably 20% by volume or less. When the content of (C ′) boron nitride nanotubes is not less than the above lower limit, heat dissipation, mechanical strength, compressibility, dielectric breakdown characteristics, and workability are effectively enhanced. When the content of (C ′) boron nitride nanotubes is not more than the above upper limit, it is easy to sufficiently cure the thermosetting material. When the content of (C ′) boron nitride nanotubes is not more than the above upper limit, the thermal conductivity and adhesiveness due to the cured product are further enhanced.

  Among the components contained in the thermosetting material, the components excluding the solvent are thermosetting materials when the thermosetting material does not contain a solvent, and the solvents when the thermosetting material contains a solvent. It is a component excluding

  From the viewpoint of effectively increasing heat dissipation and mechanical strength, the content of (C ′) boron nitride nanotubes in 100 volume% of the thermosetting material is (D) in 100 volume% of the thermosetting material. The ratio to the content of the insulating filler is preferably 0.001 or more, more preferably 0.02 or more, preferably 1.6 or less, and more preferably 1.0 or less.

((A) thermosetting compound)
(A) As thermosetting compounds, styrene compounds, phenoxy compounds, oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds and polyimide compounds Etc. (A) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  (A) As the thermosetting compound, (A1) a thermosetting compound having a molecular weight of less than 10,000 (sometimes simply referred to as (A1) thermosetting compound) may be used. (A2) 10,000 or more (A2) thermosetting compound and (A2) both thermosetting compound and a thermosetting compound having a molecular weight of (A2) may be used. May be used. (A) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  Among the components contained in the thermosetting material, the content of the (A) thermosetting compound is preferably 10% in 100% by weight of the component excluding the solvent, (C ′) boron nitride nanotube, and (D) insulating filler. %, More preferably 20% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, particularly preferably 60% by weight or less, and most preferably 50% by weight or less. is there. (A) The adhesiveness and heat resistance of hardened | cured material become still higher that content of a thermosetting compound is more than the said minimum. (A) The coating property at the time of preparation of a thermosetting material becomes it high that content of a thermosetting compound is below the said upper limit.

  Among the components contained in the thermosetting material, the components excluding the solvent, (C ′) boron nitride nanotube, and (D) the insulating filler are the components in which the thermosetting material does not contain the solvent, and (C ′) boron nitride nanotube. Is a thermosetting material, and if the thermosetting material does not contain a solvent and contains (C ′) boron nitride nanotubes, (C ′) is a component excluding boron nitride nanotubes. When the thermosetting material contains a solvent and (C ′) boron nitride nanotubes, it is a component excluding the solvent and (C ′) boron nitride nanotubes.

(A1) Thermosetting compound having a molecular weight of less than 10,000:
(A1) As a thermosetting compound, the thermosetting compound which has a cyclic ether group is mentioned. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The thermosetting compound having a cyclic ether group is preferably a thermosetting compound having an epoxy group or an oxetanyl group. (A1) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The (A1) thermosetting compound may contain (A1a) a thermosetting compound having an epoxy group (sometimes simply referred to as (A1a) a thermosetting compound), and (A1b) an oxetanyl group. A thermosetting compound (which may be simply referred to as (A1b) thermosetting compound).

  From the viewpoint of further increasing the heat resistance and moisture resistance of the cured product, the (A1) thermosetting compound preferably has an aromatic skeleton.

  The aromatic skeleton is not particularly limited, and examples thereof include naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton, and bisphenol A skeleton. From the viewpoint of further improving the cold-heat cycle characteristics and heat resistance of the cured product, a biphenyl skeleton or a fluorene skeleton is preferable.

  (A1a) The thermosetting compound includes an epoxy monomer having a bisphenol skeleton, an epoxy monomer having a dicyclopentadiene skeleton, an epoxy monomer having a naphthalene skeleton, an epoxy monomer having an adamantane skeleton, an epoxy monomer having a fluorene skeleton, and a biphenyl skeleton. Epoxy monomers having a bi (glycidyloxyphenyl) methane skeleton, epoxy monomers having a xanthene skeleton, epoxy monomers having an anthracene skeleton, and epoxy monomers having a pyrene skeleton. These hydrogenated products or modified products may be used. (A1a) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the epoxy monomer having a bisphenol skeleton include an epoxy monomer having a bisphenol A type, bisphenol F type, or bisphenol S type bisphenol skeleton.

  Examples of the epoxy monomer having a dicyclopentadiene skeleton include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

  Examples of the epoxy monomer having a naphthalene skeleton include 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidyl. Naphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, 1,2,5,6-tetraglycidylnaphthalene and the like can be mentioned.

  Examples of the epoxy monomer having an adamantane skeleton include 1,3-bis (4-glycidyloxyphenyl) adamantane and 2,2-bis (4-glycidyloxyphenyl) adamantane.

  Examples of the epoxy monomer having a fluorene skeleton include 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, and 9,9-bis (4- Glycidyloxy-3-chlorophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-bromophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-Glycidyloxy-3-methoxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dichlorophenyl) Fluorene and 9,9-bis (4-glycidyloxy-3,5-dibromophenyl) Fluorene, and the like.

  Examples of the epoxy monomer having a biphenyl skeleton include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl.

  Examples of the epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton include 1,1′-bi (2,7-glycidyloxynaphthyl) methane, 1,8′-bi (2,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,7-glycidyloxynaphthyl) methane, 1,8′-bi (3,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,5-glycidyloxynaphthyl) methane 1,8'-bi (3,5-glycidyloxynaphthyl) methane, 1,2'-bi (2,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,7-glycidyloxynaphthyl) Examples include methane and 1,2′-bi (3,5-glycidyloxynaphthyl) methane.

  Examples of the epoxy monomer having a xanthene skeleton include 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9-phenyl-9H-xanthene.

  Specific examples of the (A1b) thermosetting compound include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3-ethyl- 3-oxetanyl) methyl] ester, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, oxetane-modified phenol novolak, and the like. (A1b) Only 1 type may be used for a thermosetting compound and 2 or more types may be used together.

  From the viewpoint of further improving the heat resistance of the cured product, the (A1) thermosetting compound preferably includes a thermosetting compound having two or more cyclic ether groups.

  From the viewpoint of further improving the heat resistance of the cured product, the content of the thermosetting compound having two or more cyclic ether groups is preferably 70% by weight or more in 100% by weight of the (A1) thermosetting compound. More preferably, it is 80% by weight or more and 100% by weight or less. (A1) In 100% by weight of the thermosetting compound, the content of the thermosetting compound having two or more cyclic ether groups may be 10% by weight or more and 100% by weight or less. Further, the whole (A1) thermosetting compound may be a thermosetting compound having two or more cyclic ether groups.

  (A1) The molecular weight of the thermosetting compound is less than 10,000. (A1) The molecular weight of the thermosetting compound is preferably 200 or more, preferably 1200 or less, more preferably 600 or less, and still more preferably 550 or less. (A1) When the molecular weight of the thermosetting compound is equal to or more than the above lower limit, the adhesiveness of the surface of the cured product is lowered, and the handleability of the curable composition is further enhanced. (A1) When the molecular weight of the thermosetting compound is not more than the above upper limit, the adhesiveness of the cured product is further enhanced. Furthermore, the cured product is hard and hard to be brittle, and the adhesiveness of the cured product is further enhanced.

  In this specification, (A1) the molecular weight of the thermosetting compound is (A1) when the thermosetting compound is not a polymer, and (A1) when the structural formula of the thermosetting compound can be specified. It means the molecular weight that can be calculated from the structural formula. When the thermosetting compound (A1) is a polymer, it means the weight average molecular weight.

  Of the components contained in the thermosetting material, the content of the (A1) thermosetting compound is preferably 10% in 100% by weight of the component excluding the solvent, (C ′) boron nitride nanotube, and (D) insulating filler. %, More preferably 20% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, particularly preferably 60% by weight or less, and most preferably 50% by weight or less. is there. (A1) When the content of the thermosetting compound is not less than the above lower limit, the adhesiveness and heat resistance of the cured product are further enhanced. (A1) The coating property at the time of preparation of a thermosetting material becomes it high that content of a thermosetting compound is below the said upper limit.

(A2) Thermosetting compound having a molecular weight of 10,000 or more:
(A2) The thermosetting compound is a thermosetting compound having a molecular weight of 10,000 or more. Since the molecular weight of the (A2) thermosetting compound is 10,000 or more, the (A2) thermosetting compound is generally a polymer, and the above molecular weight generally means a weight average molecular weight.

  From the viewpoint of further improving the heat resistance and moisture resistance of the cured product, the (A2) thermosetting compound preferably has an aromatic skeleton. (A2) When the thermosetting compound is a polymer and (A2) the thermosetting compound has an aromatic skeleton, (A2) the thermosetting compound has an aromatic skeleton in any part of the whole polymer. What is necessary is just to have, it may have in the main chain frame | skeleton, and you may have in a side chain. From the viewpoint of further increasing the heat resistance of the cured product and further increasing the moisture resistance of the cured product, the (A2) thermosetting compound preferably has an aromatic skeleton in the main chain skeleton. (A2) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The aromatic skeleton is not particularly limited, and examples thereof include naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton, and bisphenol A skeleton. A biphenyl skeleton or a fluorene skeleton is preferred. In this case, the thermal cycle resistance and heat resistance of the cured product are further enhanced.

  (A2) The thermosetting compound is not particularly limited. Styrene resin, phenoxy resin, oxetane resin, epoxy resin, episulfide compound, (meth) acrylic resin, phenol resin, amino resin, unsaturated polyester resin, polyurethane resin, silicone Examples thereof include resins and polyimide resins.

  From the viewpoint of suppressing the oxidative degradation of the cured product, further improving the heat cycle resistance and heat resistance of the cured product, and further reducing the water absorption of the cured product, (A2) the thermosetting compound is a styrene resin, It is preferably a phenoxy resin or an epoxy resin, more preferably a phenoxy resin or an epoxy resin, and further preferably a phenoxy resin. In particular, use of a phenoxy resin or an epoxy resin further increases the heat resistance of the cured product. Moreover, use of a phenoxy resin further lowers the elastic modulus of the cured product and further improves the cold-heat cycle characteristics of the cured product. In addition, the (A2) thermosetting compound does not need to have cyclic ether groups, such as an epoxy group.

  As the styrene resin, specifically, a homopolymer of a styrene monomer, a copolymer of a styrene monomer and an acrylic monomer, or the like can be used. Styrene polymers having a styrene-glycidyl methacrylate structure are preferred.

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, and pn-. Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2,4-dimethyl Examples include styrene and 3,4-dichlorostyrene.

  Specifically, the phenoxy resin is, for example, a resin obtained by reacting an epihalohydrin with a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound with a divalent phenol compound.

  The phenoxy resin has a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton, or a dicyclopentadiene skeleton. It is preferable. More preferably, the phenoxy resin has a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, or a biphenyl skeleton, and at least one of the fluorene skeleton and the biphenyl skeleton. More preferably, it has a skeleton. Use of the phenoxy resin having these preferable skeletons further increases the heat resistance of the cured product.

  The epoxy resin is an epoxy resin other than the phenoxy resin. Examples of the epoxy resins include styrene skeleton-containing epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, and fluorene type epoxy resins. , Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having adamantane skeleton, epoxy resin having tricyclodecane skeleton, and epoxy resin having triazine nucleus in skeleton Etc.

  (A2) The molecular weight of the thermosetting compound is 10,000 or more. (A2) The molecular weight of the thermosetting compound is preferably 30000 or more, more preferably 40000 or more, preferably 1000000 or less, more preferably 250,000 or less. (A2) When the molecular weight of the thermosetting compound is not less than the above lower limit, the cured product is hardly thermally deteriorated. When the molecular weight of the (A2) thermosetting compound is not more than the above upper limit, the compatibility between the (A2) thermosetting compound and other components is increased. As a result, the heat resistance of the cured product is further increased.

  Of the components contained in the thermosetting material, the content of the (A2) thermosetting compound is preferably 20% in 100% by weight of the component excluding the solvent, (C ′) boron nitride nanotube, and (D) insulating filler. % Or more, more preferably 30% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less. (A2) When the content of the thermosetting compound is not less than the above lower limit, the handleability of the thermosetting material is improved. When the content of the (A2) thermosetting compound is not more than the above upper limit, dispersion of (C ′) boron nitride nanotubes and (D) insulating filler is facilitated.

((B) thermosetting agent)
(B) The thermosetting agent is not particularly limited. As the (B) thermosetting agent, an appropriate thermosetting agent capable of curing the (A) thermosetting compound can be used. In the present specification, the thermosetting agent (B) includes a curing catalyst. (B) As for a thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further increasing the heat resistance of the cured product, the (B) thermosetting agent preferably has an aromatic skeleton or an alicyclic skeleton. (B) The thermosetting agent preferably includes an amine curing agent (amine compound), an imidazole curing agent, a phenol curing agent (phenol compound) or an acid anhydride curing agent (acid anhydride), and includes an amine curing agent. Is more preferable. The acid anhydride curing agent includes an acid anhydride having an aromatic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton, It is preferable to include a water additive of an acid anhydride or a modified product of the acid anhydride.

  Examples of the amine curing agent include dicyandiamide, imidazole compounds, diaminodiphenylmethane, and diaminodiphenylsulfone. From the viewpoint of further improving the adhesiveness of the cured product, the amine curing agent is more preferably a dicyandiamide or an imidazole compound. From the viewpoint of further improving the storage stability of the curable composition, the (B) thermosetting agent preferably contains a curing agent having a melting point of 180 ° C. or higher, and an amine curing agent having a melting point of 180 ° C. or higher. More preferably.

  Examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl. 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 '-Methyl Midazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole Can be mentioned.

  Examples of the phenol curing agent include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, xylylene modified novolak, decalin modified novolak, poly ( And di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane. From the viewpoint of further enhancing the flexibility of the cured product and the flame retardancy of the cured product, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferable.

  Commercially available products of the phenol curing agent include MEH-8005, MEH-8010 and MEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Mitsubishi Chemical Corporation), LA-7052, LA-7054, and LA-7751. LA-1356 and LA-3018-50P (all of which are manufactured by DIC Corporation), PS6313 and PS6492 (all of which are manufactured by Gunei Chemical Co., Ltd.), and the like.

  Examples of the acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, a benzophenone tetracarboxylic acid anhydride, and a pyromellitic acid anhydride. , Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynyl phthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydroanhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.

  Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80. Also manufactured by Sartomer Japan), ODPA-M and PEPA (all manufactured by Manac), Ricacid MTA-10, Ricacid MTA-15, Ricacid TMTA, Ricacid TMEG-100, Ricacid TMEG-200, Ricacid TMEG-300, Ricacid TMEG-500, Ricacid TMEG-S, Ricacid TH, Ricacid HT-1A, Ricacid HH, Ricacid MH-700, Ricacid MT-500, Ricacid DSDA and Ricacid TDA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) PICLON B4400, EPICLON B650, and EPICLON B570 (all manufactured by both by DIC Corporation), and the like.

  The acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. By using these curing agents, the flexibility of the cured product and the moisture resistance and adhesion of the cured product are further increased.

  Examples of the acid anhydride having an alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid anhydride And the like.

  Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include Ricacid HNA and Ricacid HNA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Mitsubishi Chemical Corporation) and the like.

  (B) It is also preferred that the thermosetting agent is methyl nadic acid anhydride or trialkyltetrahydrophthalic anhydride. Use of methyl nadic anhydride or trialkyltetrahydrophthalic anhydride increases the water resistance of the cured product.

  Among the components contained in the thermosetting material, the content of (B) the thermosetting agent is preferably 0.1% in 100% by weight of the component excluding the solvent, (C ′) boron nitride nanotubes, and (D) the insulating filler. % By weight or more, more preferably 1% by weight or more, preferably 40% by weight or less, more preferably 25% by weight or less. (B) It is easy to fully harden a thermosetting material as content of a thermosetting agent is more than the said minimum. (B) When content of a thermosetting agent is below the said upper limit, the excess (B) thermosetting agent which does not participate in hardening becomes difficult to generate | occur | produce. For this reason, the heat resistance and adhesiveness of hardened | cured material become still higher.

((D) Insulating filler that is not a nanotube)
(D) The insulating filler may be an organic filler or an inorganic filler. From the viewpoint of effectively improving heat dissipation, the (D) insulating filler is preferably an inorganic filler. From the viewpoint of effectively improving heat dissipation, the (D) insulating filler preferably has a thermal conductivity of 10 W / m · K or more. (D) As for an insulating filler, only 1 type may be used and 2 or more types may be used together. Insulating means that the volume resistivity of the filler is 10 ⁶ Ω · cm or more.

  From the viewpoint of further improving the heat dissipation of the cured product, the thermal conductivity of the (D) insulating filler is preferably 10 W / m · K or more, more preferably 15 W / m · K or more, and even more preferably 20 W / m ·. K or more. (D) The upper limit of the thermal conductivity of the insulating filler is not particularly limited. Inorganic fillers having a thermal conductivity of about 300 W / m · K are widely known, and inorganic fillers having a thermal conductivity of about 200 W / m · K are easily available.

  (D) The material of the insulating filler is preferably alumina, synthetic magnesite, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide, alumina, boron nitride, aluminum nitride, silicon nitride, More preferred is silicon carbide, zinc oxide or magnesium oxide. Use of these preferable insulating fillers further enhances the heat dissipation of the cured product.

  (D) It is preferable that an insulating filler is a spherical particle or the spherical particle which the independent insulating filler aggregated. By using these insulating fillers, the heat dissipation of the cured product is further enhanced. The aspect ratio of the spherical particles is 2 or less.

  (D) The new Mohs hardness of the insulating filler material is preferably 12 or less, more preferably 9 or less. (D) When the new Mohs hardness of the insulating filler material is 9 or less, the workability of the cured product is further enhanced.

  From the viewpoint of further improving the workability of the cured product, the material of the (D) insulating filler is preferably synthetic magnesite, crystalline silica, zinc oxide, or magnesium oxide. The new Mohs hardness of these inorganic filler materials is 9 or less.

  From the viewpoint of effectively improving heat dissipation, the average particle diameter of the (D) insulating filler is preferably 1 μm or more, and preferably 100 μm or less. When the average particle diameter is not less than the above lower limit, (D) the insulating filler can be easily filled at a high density. When the average particle size is not more than the above upper limit, the withstand voltage of the cured product is further enhanced.

  The “average particle diameter” is an average particle diameter obtained from a volume average particle size distribution measurement result measured by a laser diffraction particle size distribution measuring apparatus.

  Among the components contained in the thermosetting material, the content of the (D) insulating filler is preferably 40% by volume or more, more preferably 50% by volume or more, preferably 90% by volume, in 100% by volume of the component excluding the solvent. Hereinafter, it is more preferably 80% by volume or less. (D) The heat dissipation of hardened | cured material becomes high effectively that content of an insulating filler is more than the said minimum and below the said upper limit.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

(Examples 1-9)
Preparation of thermosetting material:
44 parts by weight of a bisphenol A type phenoxy resin as a polymer, 33 parts by weight of a bisphenol A type epoxy resin as an epoxy resin, 17 parts by weight of an alicyclic skeleton acid anhydride and dicyandiamide as an curing agent, and an epoxy silane coupling agent as an additive A paste (thermosetting material) was obtained by blending 16 parts by weight.

Production of first and second metal composites:
One surface of the copper substrate was protected with a polyimide film, and the other surface was degreased with acetone. Next, the copper surface was cleaned and roughened by etching with a 5% sulfuric acid aqueous solution for 1 minute by ultrasonic waves. Next, the copper substrate is immersed in an aqueous solution containing 0.01% by weight of palladium sulfate, and dimethylamine borane is further added to precipitate palladium, followed by filtration and washing, and a copper substrate carrying palladium only on one surface. Got.

  Next, 10 g of a copper substrate carrying palladium was placed in 500 mL of ion-exchanged water containing 1% by weight of sodium succinate. Sulfuric acid was added to the aqueous solution containing the copper substrate, and the aqueous solution containing the copper substrate was adjusted to pH 5.

  A nickel plating solution containing 20% by weight of nickel sulfate, 30% by weight of sodium hypophosphite, and 5% by weight of sodium hydroxide was prepared as a nickel plating solution.

  A nickel plating solution was continuously dropped into an aqueous solution containing a copper substrate heated to 80 ° C. and stirred for 5 minutes to obtain a copper substrate carrying nano-sized nickel.

  Next, a mixture of boron powder (purity 99.995%) and magnesium oxide powder (purity 99%) (molar ratio 1: 1) was pulverized with a ball mill for 6 hours. The obtained finely divided material was placed apart in a boron nitride boat, and the boat was placed on a graphite support.

  A mixture of boron powder and magnesium oxide powder was heated to 1300 ° C. using a high-frequency induction heating furnace, and the generated vapor mixture of boron oxide and magnesium was transferred toward the copper substrate with argon gas. When the heating temperature reaches 1300 ° C., ammonia gas is allowed to flow into the copper substrate, and after reacting with boron oxide in the mixed vapor for 200 minutes, the heating furnace is gradually cooled to a room temperature of 30 ° C. or less, and the metal composite (Copper substrate covered with boron nitride nanotubes grown vertically on one surface of a copper substrate) was produced. In the obtained BNNT, the average diameter was 10 nm and the average length was 5 μm.

  The metal composite was impregnated with a thermosetting material and dried in an oven at 90 ° C. for 30 minutes to obtain a first metal composite and a second metal composite.

Production of insulating material sheet:
Production of boron nitride nanotubes:
Boron, magnesium oxide and iron oxide were put in a boron nitride crucible in a molar ratio of 2: 1: 1, and the crucible was heated to 1300 ° C. in a high-frequency induction heating furnace (heating step 1). Ammonia gas was introduced into the product and heated at 1200 ° C. for 2 hours (heating step 2). The obtained white solid was washed with concentrated hydrochloric acid, washed with ion exchange water until neutral, and then dried to obtain boron nitride nanotubes (BNNT). The obtained BNNT had an average diameter of 10 nm and an average length of 50 μm.

  Boron nitride nanotubes and insulating filler were added to the thermosetting material at a blending ratio (unit: volume%) shown in Table 1 below, and kneaded with a homodisper type stirrer to obtain a paste (thermosetting material).

  The thermosetting material was applied to a release PET sheet having a thickness of 50 μm so as to have the thickness shown in Table 1, and dried in an oven at 90 ° C. for 30 minutes to produce an insulating material sheet on the PET sheet. .

Production of laminate:
The insulating material sheet is sandwiched between the first metal composite and the second metal composite, and the pressure of 4 MPa is maintained with a vacuum press machine at 120 ° C. for 1 hour, and further at 200 ° C. for 1 hour. Was press-cured to form an insulating material portion, and a laminate was produced.

(Comparative Example 1)
Preparation of thermosetting material:
44 parts by weight of a bisphenol A type phenoxy resin as a polymer, 33 parts by weight of a bisphenol A type epoxy resin as an epoxy resin, an alicyclic skeleton acid anhydride as a curing agent (“Ricacid MH-700” manufactured by Shin Nippon Rika Co., Ltd.) and dicyandiamide A total of 17 parts by weight and 16 parts by weight of an epoxy silane coupling agent as an additive were blended to prepare a matrix resin. Insulating fillers were added to the matrix resin in the proportions shown in Table 1 below (the blending unit was volume%) and kneaded with a homodisper type stirrer to obtain a paste (thermosetting material).

Production of insulation material:
The thermosetting material was applied to a release PET sheet having a thickness of 50 μm so as to have the thickness shown in Table 1, and dried in an oven at 90 ° C. for 30 minutes to produce an insulating material portion on the PET sheet. .

Production of laminate:
The insulating material part is sandwiched between the first metal composite and the second metal composite, and the pressure is maintained at 4 MPa with a vacuum press machine at 120 ° C. for 1 hour, and further at 200 ° C. for 1 hour. Was press-cured to prepare a laminate.

(Comparative Example 2)
A laminate was produced in the same manner as in Example 1 except that the boron nitride nanotubes in the insulating material part were changed to carbon nanotubes.

(Evaluation)
(1) Heat dissipation property The copper foil surface of the obtained laminate was pressed against the same size of a heating element with a smooth surface controlled at 60 ° C. with a pressure of 196 N / cm ² . The temperature of the surface of the aluminum plate was measured with a thermocouple. The heat dissipation was determined according to the following criteria.

[Criteria for heat dissipation]
A: The temperature difference between the surface of the heating element and the aluminum plate is 3 ° C. or less. ○: The temperature difference between the surface of the heating element and the aluminum plate exceeds 3 ° C. and 6 ° C. or less. Δ: The surface difference between the heating element and the aluminum plate. Temperature difference exceeds 6 ° C and 10 ° C or less ×: Temperature difference between the surface of the heating element and the aluminum plate exceeds 10 ° C

(2) Mechanical strength A bending test was carried out by the three-point fulcrum method using the obtained laminate. The test piece was subjected to 1000 cycles under the condition that the test piece was bent at a depth of 20 μm once per second, and then whether or not the cured sheet was peeled off from the substrate was observed. Mechanical strength was determined according to the following criteria.

[Judgment criteria for mechanical strength]
◎: Occurrence of peeling at less than 5% of area or no occurrence of peeling ○: Occurrence of peeling at 5% or more and less than 10% of area △: Occurrence of peeling at or above 10% of area, less than 20% ×: Area of Occurrence of peeling at less than 10%

(3) Dielectric breakdown voltage (withstand voltage)
Using a withstand voltage tester ("MODEL7473" manufactured by EXTECH Electronics), an alternating voltage was applied between the laminates so that the voltage increased at a rate of 1 kV / second. The voltage at which the insulating material part was broken was defined as the breakdown voltage. The dielectric breakdown voltage was determined according to the following criteria.

[Criteria for dielectric breakdown voltage]
◎: 90 kV / mm or more ○: 60 kV / mm or more, less than 90 kV / mm Δ: 30 kV / mm or more, less than 60 kV / mm ×: less than 30 kV / mm

DESCRIPTION OF SYMBOLS 1 ... Laminated body 2 ... Hardened | cured material sheet 3 ... 1st metal composite 4 ... 2nd metal composite 11 ... Hardened | cured material part (hardened | cured material part of a thermosetting component)
DESCRIPTION OF SYMBOLS 12 ... Boron nitride nanotube 13 ... Insulating filler 21 ... 1st metal body 22 ... Boron nitride nanotube 31 ... 2nd metal body 32 ... Boron nitride nanotube

Claims (6)

A metal complex;
An insulating material part,
The metal composite has a metal body and a plurality of boron nitride nanotubes disposed on a surface of the metal body;
On the surface of the insulating material portion, the metal composite is disposed from the boron nitride nanotube side,
The laminated body in which the said insulating material part contains the hardened | cured material part of the thermosetting component containing a thermosetting compound and a thermosetting agent, and the insulating filler which is not a nanotube.   The laminate according to claim 1, wherein the boron nitride nanotube is in contact with the surface of the metal body at one end side in a length direction of the boron nitride nanotube.   The ratio of the total volume of the boron nitride nanotubes in the metal composite to the total volume of the insulating filler in the insulating material part is 0.02 or more and 2.0 or less. Laminated body.   The laminate according to any one of claims 1 to 3, wherein the cured product portion in the insulating material portion is interposed between the plurality of boron nitride nanotubes in the metal composite. The average diameter of the boron nitride nanotube is 2 nm or more and 300 nm or less,
The laminated body of any one of Claims 1-4 whose average length of the said boron nitride nanotube is 1 micrometer or more and 200 micrometers or less.   The laminate according to any one of claims 1 to 5, wherein the insulating material part includes boron nitride nanotubes.

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