JP5520183B2 - Resin composition, resin sheet and laminated structure - Google Patents

Description

  The present invention relates to a paste-like resin composition and a resin sheet used for bonding a thermal conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer, and more specifically, has high adhesiveness, In addition, the present invention relates to a resin composition and a resin sheet that have good water resistance and moisture resistance of a cured product after curing, and a laminated structure using the resin composition or resin sheet.

  In electronic devices and communication devices, printed wiring boards having an insulating layer are used. The insulating layer is formed using a paste-like or sheet-like insulating adhesive material.

  As an example of the above-mentioned insulating adhesive material, the following patent document 1 discloses an insulating adhesive in which a glass cloth is impregnated with an adhesive composition containing an epoxy resin, an epoxy resin curing agent, a curing accelerator, an elastomer and an inorganic filler. A sheet is disclosed.

  Insulating adhesive materials that do not contain glass cloth are also known. For example, the example of Patent Document 2 below includes an insulating adhesive containing bisphenol A type epoxy resin, phenoxy resin, phenol novolak, 1-cyanoethyl-2-phenylimidazole, γ-glycidoxypropyltrimethoxysilane, and alumina. Agents are disclosed. Here, examples of the epoxy resin curing agent include tertiary amines, acid anhydrides, imidazole compounds, polyphenol resins, and mask isocyanates.

JP 2006-342238 A JP-A-8-332696

  In the insulating adhesive sheet described in Patent Document 1, a glass cloth is used in order to improve handling properties. With an insulating adhesive sheet including glass cloth, it is difficult to make a thin film, and various processes such as laser processing or drilling are difficult. Moreover, since the heat conductivity of the hardened | cured material of the insulation adhesive sheet containing a glass cloth is comparatively low, sufficient heat dissipation may not be obtained. Furthermore, special impregnation equipment must be prepared for impregnating the glass cloth with the adhesive composition.

  In the insulating adhesive described in Patent Document 2, since glass cloth is not used, the sheet itself is not self-supporting in an uncured state. For this reason, the handling property of the insulating adhesive is low.

  Furthermore, since the silane coupling agent is not used in the insulating adhesive sheet described in Patent Document 1, the adhesiveness of the insulating adhesive sheet is low, or the water resistance and moisture resistance of the cured product after curing are low. There is. In addition, although γ-glycidoxypropyltrimethoxysilane is used in the insulating adhesive described in Patent Document 2, the adhesiveness of the insulating adhesive and the cured product can be obtained only by using this silane coupling agent. It is difficult to make the water resistance and moisture resistance sufficiently high.

  An object of the present invention is used to adhere a heat conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer, and has good adhesion to a member to be bonded. It is providing the resin composition and resin sheet which are excellent in water resistance and moisture resistance, and the laminated structure using this resin composition or resin sheet.

  A limited object of the present invention is not only good adhesion and water resistance and moisture resistance of a cured product, but also a resin sheet excellent in handling properties in an uncured state, and the resin sheet It is providing the laminated structure using this.

  According to a wide aspect of the present invention, there is provided a paste-like resin composition used for bonding a thermal conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer, wherein an epoxy group or an oxetane group is present. A resin composition comprising a curable compound having, a curing agent, a filler, a first silane coupling agent having an epoxy group, and a second silane coupling agent having an alkyl group having 4 to 12 carbon atoms. Is provided.

  According to another broad aspect of the present invention, there is provided a resin sheet used for adhering a thermal conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer, and having a weight average molecular weight of 10,000. A polymer having a weight average molecular weight of less than 10,000, a curable compound having an epoxy group or an oxetane group, a curing agent, a filler, a first silane coupling agent having an epoxy group, and carbon A resin sheet comprising a second silane coupling agent having an alkyl group of several 4 to 12 is provided.

  The resin composition and resin sheet according to the present invention are used to adhere a heat conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer, and are an insulating resin composition or resin sheet in the form of a paste. Material. The resin composition according to the present invention and the resin sheet according to the present invention are paste-like or sheet-like insulating materials. Each of the resin composition according to the present invention and the resin sheet according to the present invention includes a curable compound having an epoxy group or an oxetane group, a curing agent, a filler, and a first silane coupling agent having an epoxy group, And a second silane coupling agent having an alkyl group having 4 to 12 carbon atoms.

  The second silane coupling agent preferably has a linear alkyl group having 6 to 10 carbon atoms.

  The filler is preferably at least one selected from the group consisting of alumina, synthetic magnesite, crystalline silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide and magnesium oxide.

  The polymer is preferably a polymer having an aromatic skeleton and a weight average molecular weight of 30,000 or more.

  The curable compound has an aromatic skeleton and an epoxy group, and has an epoxy monomer having a weight average molecular weight of 600 or less, or has an aromatic skeleton and an oxetane group, and has a weight average molecular weight of 600 or less. It preferably contains an oxetane monomer.

  Content of the polymer in a total of 100% by weight of resin components in the resin sheet containing the polymer, the curable compound, the curing agent, the first silane coupling agent, and the second silane coupling agent. Is preferably 20 wt% or more and 60 wt% or less, and the content of the curable compound is preferably 10 wt% or more and 60 wt% or less.

  The polymer is preferably a phenoxy resin.

  The curing agent is preferably a phenol resin, dicyandiamide, an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. The curing agent is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or a fat obtained by an addition reaction of a terpene compound and maleic anhydride. An acid anhydride having a cyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is preferable. The curing agent is preferably an acid anhydride represented by any one of the following formulas (1) to (4).

  In said formula (4), R1 and R2 show hydrogen, a C1-C5 alkyl group, or a hydroxyl group, respectively.

  The laminated structure according to the present invention includes a heat conductor having a thermal conductivity of 10 W / m · K or more, an insulating layer laminated on at least one surface of the heat conductor, and the heat conduction of the insulating layer. A conductive layer laminated on a surface opposite to the surface on which the body is laminated, and the insulating layer is formed by curing a resin composition or a resin sheet configured according to the present invention. .

  The heat conductor is preferably a metal.

  Each of the resin composition according to the present invention and the resin sheet according to the present invention includes a curable compound having an epoxy group or an oxetane group, a curing agent, a filler, and a first silane coupling agent having an epoxy group, Since it contains the 2nd silane coupling agent which has a C4-C12 alkyl group, the adhesiveness with respect to the adhesion target member of a resin composition and a resin sheet can be made favorable. Furthermore, the water resistance and moisture resistance of the cured product after curing can be increased.

FIG. 1 is a partially cutaway front sectional view schematically showing a laminated structure according to an embodiment of the present invention.

  Details of the present invention will be described below.

  Both the resin composition according to the present invention and the resin sheet according to the present invention are used for bonding a thermal conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer.

  Each of the resin composition according to the present invention and the resin sheet according to the present invention has a curable compound (B) having an epoxy group or an oxetane group, a curing agent (C), a filler (D), and an epoxy group. 1st silane coupling agent (E1) and 2nd silane coupling agent (E2) which has a C4-C12 alkyl group are included. The resin sheet according to the present invention further includes a polymer (A) having a weight average molecular weight of 10,000 or more. The resin composition according to the present invention may or may not contain the polymer (A) having a weight average molecular weight of 10,000 or more. In the resin sheet according to the present invention, the curable compound (B) having an epoxy group or an oxetane group has a weight average molecular weight of less than 10,000.

  The resin composition and the cured product of the resin sheet used for the above applications are required to have high thermal conductivity. Therefore, the filler (D) is used.

  By adopting the above composition, it is possible to increase the adhesion of the resin composition and the resin sheet to the conductive layer and the heat conductor, which are members to be bonded. As a result, the adhesiveness with respect to the electrically conductive layer and heat conductor which are the adhesion object members of the hardened | cured material of a resin composition and the hardened | cured material of a resin sheet becomes high. Furthermore, the water resistance and moisture resistance of the cured product of the resin composition and the cured product of the resin sheet can be increased. Furthermore, the handleability of the resin sheet in an uncured state can be enhanced by employing the above composition. Resin sheets used for the above applications are required to have high handling properties in an uncured state.

  Hereinafter, first, details of each component contained in the resin composition according to the present invention and the resin sheet according to the present invention will be described.

(Polymer (A))
The polymer (A) contained in the resin sheet according to the present invention is not particularly limited as long as the weight average molecular weight is 10,000 or more. The polymer (A) preferably has an aromatic skeleton. In this case, the heat resistance of the cured product is further increased. When the polymer (A) has an aromatic skeleton, the aromatic skeleton may be included in any part of the entire polymer, may be included in the main chain skeleton, and may be present in the side chain. You may do it. The polymer (A) preferably has an aromatic skeleton in the main chain skeleton. In this case, the heat resistance of the cured product is further increased. As for a polymer (A), only 1 type may be used and 2 or more types may be used together.

  The aromatic skeleton is not particularly limited. Specific examples of the aromatic skeleton include naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton, and bisphenol A skeleton. Of these, a biphenyl skeleton or a fluorene skeleton is preferable. In this case, the heat resistance of the cured product is further increased.

  As the polymer (A), a curable resin such as a thermoplastic resin and a thermosetting resin can be used.

  The thermoplastic resin and thermosetting resin are not particularly limited. Examples of the thermoplastic resin and thermosetting resin include thermoplastic resins such as polyphenylene sulfide, polyarylate, polysulfone, polyethersulfone, polyetheretherketone, and polyetherketone. In addition, as the thermoplastic resin and the thermosetting resin, thermoplastic polyimide, thermosetting polyimide, benzoxazine, and a heat-resistant resin group called super engineering plastics such as a reaction product of polybenzoxazole and benzoxazine, etc. Can be used. As for the said thermoplastic resin and the said thermosetting resin, only 1 type may respectively be used and 2 or more types may be used together. Either one of a thermoplastic resin and a thermosetting resin may be used, and a thermoplastic resin and a thermosetting resin may be used in combination.

  The polymer (A) is preferably a styrene polymer, a (meth) acrylic polymer or a phenoxy resin, and more preferably a phenoxy resin. By using this preferable polymer, it is possible to prevent oxidative deterioration of the cured product and to further improve the heat resistance. In particular, the heat resistance of the cured product can be further enhanced by using a phenoxy resin.

  Specifically, a homopolymer of a styrene monomer, a copolymer of a styrene monomer and an acrylic monomer, or the like can be used as the styrene polymer. Among these, a styrene polymer having a styrene-glycidyl methacrylate structure is preferable.

  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.

  Examples of the acrylic monomer include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-2-ethylhexyl, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, Examples include butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. It is done.

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

  The phenoxy resin comprises 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, and a dicyclopentadiene skeleton. It is preferred to have at least one skeleton selected from the group. Among these, the phenoxy resin preferably has at least one skeleton selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, and a biphenyl skeleton. Preferably, it has at least one skeleton of a fluorene skeleton and a biphenyl skeleton. Use of the phenoxy resin having these preferable skeletons further increases the heat resistance of the cured product.

  The phenoxy resin preferably has a polycyclic aromatic skeleton in the main chain. The phenoxy resin more preferably has at least one skeleton of the skeletons represented by the following formulas (11) to (16) in the main chain.

In the above formula (11), R ₁ may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and X ₁ is a single bond, having 1 to 1 carbon atoms. 7 divalent hydrocarbon group, —O—, —S—, —SO ₂ —, or —CO—.

In the above formula (12), R _1a may be the same or different and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and R ₂ is a hydrogen atom, carbon number 1 10 is a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, R ₃ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 0 to 5.

In the above formula (13), R _1b may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and R ₄ is the same or different from each other. It is a hydrogen atom, a C1-C10 hydrocarbon group, or a halogen atom, and l is an integer of 0-4.

In the above formula (15), _{R 5} and _{R 6} is a hydrogen atom, an alkyl group or a halogen atom having 1 to 5 carbon atoms, _{X 2} is _{-SO 2 -, - CH 2 -} , - C (CH 3) 2 -Or -O-, and k is 0 or 1.

  As the polymer (A), for example, a phenoxy resin represented by the following formula (17) or the following formula (18) is suitably used.

In the above formula (17), A ₁ has a structure represented by any _one of the above formulas (11) to (13), and the structure thereof is the structure represented by the above formula (11) is 0 to 0. 60 mol%, the structure is 5 to 95 mol% of the formula (12), and a structure is 5 to 95 mol% of the formula (13), _{a 2} is a hydrogen atom, or the formula a group represented by (14), _{n 1} is a number of 25 to 500 in average. In the formula (17), the structure represented by the formula (11) may not be included.

In the above formula (18), A ₃ has a structure represented by the above formula (15) or the above formula (16), and n ₂ is a value of at least 21 or more.

  The glass transition temperature Tg of the polymer (A) is preferably 60 ° C. or higher, more preferably 90 ° C. or higher, preferably 200 ° C. or lower, more preferably 180 ° C. or lower. When the Tg of the polymer (A) is not less than the above lower limit, the resin is hardly thermally deteriorated. When the Tg of the polymer (A) is not more than the above upper limit, the compatibility between the polymer (A) and another resin is increased. As a result, the handling property of the resin sheet in an uncured state is further improved, and the heat resistance of the cured product is further increased.

  When the polymer (A) is a phenoxy resin, the glass transition temperature Tg of the phenoxy resin is preferably 95 ° C or higher, more preferably 110 ° C or higher, preferably 200 ° C or lower, more preferably 180 ° C or lower. When the Tg of the phenoxy resin is not less than the above lower limit, the thermal deterioration of the resin can be further suppressed. When the Tg of the phenoxy resin is not more than the above upper limit, the compatibility between the phenoxy resin and the other resin is increased. As a result, the handling property of the resin sheet in the uncured state and the heat resistance of the cured product are further enhanced.

  The weight average molecular weight of the polymer (A) is 10,000 or more. The weight average molecular weight of the polymer (A) is preferably 30000 or more, more preferably 40000 or more, preferably 1000000 or less, more preferably 250,000 or less. When the weight average molecular weight of the polymer (A) is not less than the above lower limit, the resin composition or the resin sheet is hardly thermally deteriorated. When the weight average molecular weight of the polymer (A) is not more than the above upper limit, the compatibility between the polymer (A) and another resin is increased. As a result, the handling property of the resin sheet in an uncured state is further improved, and the heat resistance of the cured product is further increased.

  In the present specification, the weight average molecular weight means a molecular weight that can be calculated from the structural formula when the polymer is not a polymer and when the structural formula can be specified. In the case of a polymer, it means a weight average molecular weight.

  The polymer (A) may be added as a raw material, and is a polymer produced by utilizing a reaction in each step such as stirring, coating, and drying during the production of the resin composition or resin sheet according to the present invention. It may be.

  In the resin sheet which concerns on this invention, a polymer (A), a sclerosing | hardenable compound (B), a hardening | curing agent (C), a 1st silane coupling agent (E1), and a 2nd silane coupling agent (E2) are included. The content of the polymer (A) is 20% by weight or more and 60% by weight or less in the total 100% by weight of the total resin components (hereinafter sometimes abbreviated as “total resin component X”) contained in the resin sheet. It is preferable. The content of the polymer (A) in the total 100% by weight of all the resin components X in the resin sheet is more preferably 30% by weight or more, and more preferably 50% by weight or less. When the content of the polymer (A) is not less than the above lower limit, the handleability of the resin sheet in an uncured state is further improved. When the content of the polymer (A) is not more than the above upper limit, the filler (D) can be easily dispersed. The total resin component X means the polymer (A), the curable compound (B), the curing agent (C), the first silane coupling agent (E1), the second silane coupling agent (E2), and necessary. The sum of other resin components added according to the above. The total resin component X does not contain the filler (D). In addition, when the resin composition which concerns on this invention does not contain a polymer (A), all the resin components X do not contain a polymer (A), a curable compound (B), a hardening | curing agent (C), and 1st. The silane coupling agent (E1) and the second silane coupling agent (E2).

  The resin composition according to the present invention may not contain the polymer (A). When the resin composition according to the present invention includes the polymer (A), the content of the polymer (A) is preferably 60% by weight or less, more preferably 50% in the total 100% by weight of the total resin component X. % By weight or less. The lower limit of the content of the polymer (A) in the total 100% by weight of the total resin component X in the resin composition is not particularly limited, but the content of the polymer (A) is, for example, 0.1% by weight or more. When the content of the polymer (A) is not more than the above upper limit, the dispersion of the filler (D) is facilitated, and the coatability of the resin composition is further increased.

(Curable compound having epoxy group or oxetane group (B))
The curable compound (B) contained in the resin composition and the resin sheet according to the present invention is not particularly limited as long as it has an epoxy group or an oxetane group (oxetanyl group). However, the weight average molecular weight of the curable compound (B) contained in the resin sheet according to the present invention is less than 10,000. The weight average molecular weight of the curable compound (B) contained in the resin composition according to the present invention may be 10,000 or more, but is preferably less than 10,000. The curable compound (B) having a weight average molecular weight of less than 10,000 is different from the polymer (A) having a weight average molecular weight of 10,000 or more. Further, the curable compound (B) does not include the silane coupling agent (E1) having an epoxy group. As the curable compound (B) having an epoxy group or an oxetane group, a conventionally known epoxy compound or oxetane compound can be used. The curable compound (B) is cured by the action of the curing agent (C). As for a curable compound (B), only 1 type may be used and 2 or more types may be used together.

  The curable compound (B) may contain an epoxy compound (B1) having an epoxy group, or may contain an oxetane compound (B2) having an oxetane group.

  From the viewpoint of further improving the heat resistance and dielectric breakdown characteristics of the cured product, the curable compound (B) preferably has an aromatic skeleton.

  Specific examples of the epoxy compound (B1) having an epoxy group include 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, and an epoxy having a fluorene skeleton. Examples of the monomer include an epoxy monomer having a biphenyl skeleton, an epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton, an epoxy monomer having a xanthene skeleton, an epoxy monomer having an anthracene skeleton, and an epoxy monomer having a pyrene skeleton. These hydrogenated products or modified products may be used. As for an epoxy compound (B1), 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 oxetane compound (B2) having an oxetane group include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylate bis [(3- Ethyl-3-oxetanyl) methyl] ester, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and oxetane-modified phenol novolac. As for an oxetane compound (B2), only 1 type may be used and 2 or more types may be used together.

  The weight average molecular weight of the curable compound (B) is preferably less than 10,000. The weight average molecular weight of the curable compound (B) is preferably 200 or more, more preferably 600 or less, and still more preferably 550 or less. When the weight average molecular weight of the curable compound (B) is not less than the above lower limit, the volatility of the curable compound (B) is lowered, and the handleability of the resin composition and the resin sheet is further enhanced. When the weight average molecular weight of the curable compound (B) is not more than the above upper limit, the adhesiveness between the resin composition and the resin sheet is further enhanced. Furthermore, the resin sheet is difficult to become hard and brittle.

  In the resin sheet according to the present invention, the content of the curable compound (B) is preferably 10% by weight or more and 60% by weight or less in the total 100% by weight of the total resin component X. The content of the curable compound (B) in the total 100% by weight of all the resin components X in the resin sheet is more preferably 20% by weight or more, and more preferably 50% by weight or less. When the content of the curable compound (B) is not less than the above lower limit, the adhesiveness of the resin sheet and the heat resistance of the cured product are further enhanced. When the content of the curable compound (B) is not more than the above upper limit, the handleability of the resin sheet is further enhanced.

  In the resin composition according to the present invention, the content of the curable compound (B) is preferably 10% by weight or more and 80% by weight or less in the total 100% by weight of the total resin component X. The content of the curable compound (B) in 100% by weight of the total resin component X in the resin composition is more preferably 20% by weight or more, and more preferably 70% by weight or less. When the content of the curable compound (B) is at least the above lower limit, the adhesiveness of the resin composition and the heat resistance of the cured product are further enhanced. When the content of the curable compound (B) is not more than the above upper limit, the coatability of the resin composition is further enhanced.

  The curable compound (B) has an aromatic skeleton and an epoxy group and has an epoxy monomer (B1b) having a weight average molecular weight of 600 or less, or an aromatic skeleton and an oxetane group, and has a weight average molecular weight. It is preferable to contain the oxetane monomer (B2b) whose is is 600 or less.

  It is preferable that a curable compound (B) contains an epoxy monomer (B1b) or an oxetane monomer (B2b) in 40 to 100 weight%. It is particularly preferable that the curable compound (B) contains the epoxy monomer (B1b) or the oxetane monomer (B2b) more preferably 60% by weight or more, and still more preferably 80% by weight or more. When the content of the epoxy monomer (B1b) and the oxetane monomer (B2b) is not less than the above lower limit, the flexibility of the resin sheet, the adhesiveness of the resin composition and the resin sheet, and the heat resistance of the cured product are further enhanced.

(Curing agent (C))
The curing agent (C) contained in the resin composition and the resin sheet according to the present invention is not particularly limited as long as the resin composition or the resin sheet can be cured. The curing agent (C) is preferably a thermosetting agent. As for a hardening | curing agent (C), only 1 type may be used and 2 or more types may be used together.

  The curing agent (C) is preferably a phenol resin, dicyandiamide, an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. By using these curing agents, a cured product having an excellent balance of heat resistance, moisture resistance and electrical properties can be obtained. These curing agents are thermosetting agents.

  The phenol resin is not particularly limited. Specific examples of the phenol resin 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, Examples include poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane. Among these, from the viewpoint of further enhancing the flexibility of the resin sheet 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 phenol resins include MEH-8005, MEH-8010 and NEH-8015 (all of which are made by Meiwa Kasei Co., Ltd.), YLH903 (Japan Epoxy Resin Co., Ltd. (merged with Mitsubishi Chemical on April 1, 2010)) Product), LA-7052, LA-7054, LA-7751, LA-1356 and LA-3018-50P (all of which are manufactured by DIC), PS6313 and PS6492 (manufactured by Gunei Chemical Co., Ltd.), and the like.

  An acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is not particularly limited. Examples of the acid anhydride having an aromatic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, benzophenone tetracarboxylic acid anhydride, pyromellitic acid anhydride, Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydrophthalic anhydride Examples include acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Of these, methyl nadic acid anhydride or trialkyltetrahydrophthalic anhydride is preferable. By using methyl nadic acid anhydride or trialkyltetrahydrophthalic anhydride, the water resistance of the cured product can be increased.

  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 (any of the above 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 DIC Corporation).

  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 Japan Epoxy Resin Co., Ltd.) and the like.

  The curing agent (C) is more preferably an acid anhydride represented by any of the following formulas (1) to (4) or dicyandiamide. Moreover, it is preferable that a hardening | curing agent (C) is an acid anhydride represented by either of following formula (1)-(4). By using this preferable curing agent, the flexibility of the cured product and the moisture resistance of the cured product, and the adhesiveness of the resin composition and the resin sheet are further enhanced.

  In said formula (4), R1 and R2 show hydrogen, a C1-C5 alkyl group, or a hydroxyl group, respectively.

  In order to adjust the curing speed or the physical properties of the cured product, the curing agent and the curing accelerator may be used in combination.

  The said hardening accelerator is not specifically limited. Specific examples of the curing accelerator include tertiary amines, imidazoles, imidazolines, triazines, organic phosphorus compounds, quaternary phosphonium salts and diazabicycloalkenes such as organic acid salts. Examples of the curing accelerator include organometallic compounds, quaternary ammonium salts, metal halides, and the like. Examples of the organometallic compounds include zinc octylate, tin octylate and aluminum acetylacetone complex.

  Examples of the curing accelerator include a high melting point imidazole curing accelerator, a high melting point dispersion type latent curing accelerator, a microcapsule type latent curing accelerator, an amine salt type latent curing accelerator, and a high temperature dissociation type and thermal cation. A polymerization type latent curing accelerator or the like can be used. As for the said hardening accelerator, only 1 type may be used and 2 or more types may be used together.

  Examples of the high melting point dispersion type latent accelerator include amine addition type accelerators in which dicyandiamide or amine is added to an epoxy monomer or the like. Examples of the microcapsule type latent accelerator include a microcapsule type latent accelerator in which the surface of an imidazole, phosphorus or phosphine accelerator is coated with a polymer. Examples of the high-temperature dissociation type and thermal cationic polymerization type latent curing accelerator include Lewis acid salts and Bronsted acid salts.

  The curing accelerator is preferably a high melting point imidazole curing accelerator. By using a high melting point imidazole curing accelerator, the reaction system can be easily controlled, and the curing rate of the resin composition and the resin sheet, and the physical properties of the cured product can be more easily adjusted. A high-melting-point curing accelerator having a melting point of 100 ° C. or higher is excellent in handleability. Accordingly, the melting accelerator preferably has a melting point of 100 ° C. or higher.

In the resin sheet which concerns on this invention, it is preferable that content of a hardening | curing agent (C) is 10 to 40 weight% in the total 100 weight% of the said all resin component X. FIG. In the total 100% by weight of all resin components X in the resin sheet, the content of the curing agent (C) is more preferably 12% by weight or more, and more preferably 25% by weight or less. It is easy to fully harden a resin sheet as content of a hardening | curing agent (C) is more than the said minimum. When the content of the curing agent (C) is not more than the above upper limit, it becomes difficult to generate an excessive curing agent (C) that does not participate in curing. For this reason, the heat resistance of hardened | cured material and the adhesiveness of a resin sheet become still higher.
It is preferable.

  In the resin composition according to the present invention, the content of the curing agent (C) is preferably 10% by weight or more and 50% by weight or less in the total 100% by weight of the total resin component X. In the total 100% by weight of all resin components X in the resin composition, the content of the curing agent (C) is more preferably 20% by weight or more, and more preferably 40% by weight or less. It is easy to fully harden a resin composition as content of a hardening | curing agent (C) is more than the said minimum. When the content of the curing agent (C) is not more than the above upper limit, it becomes difficult to generate an excessive curing agent (C) that does not participate in curing. For this reason, the heat resistance of hardened | cured material and the adhesiveness of a resin composition become still higher.

(Filler (D))
The filler (D) contained in the resin composition and resin sheet according to the present invention is not particularly limited. A conventionally well-known filler can be used as a filler (D). As for a filler (D), only 1 type may be used and 2 or more types may be used together.

  The thermal conductivity of the filler (D) is preferably 10 W / m · K or more. By using this filler, the thermal conductivity of the cured product can be increased. As a result, the heat dissipation of the cured product is increased. When the thermal conductivity of the filler (D) is smaller than 10 W / m · K, it is difficult to sufficiently increase the thermal conductivity of the cured product. The thermal conductivity of the filler (D) is preferably 15 W / m · K or more, more preferably 20 W / m · K or more. The upper limit of the thermal conductivity of the filler (D) 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.

  From the viewpoint of further improving the heat dissipation of the cured product, the filler (D) is preferably an inorganic filler.

  The filler (D) is at least one selected from the group consisting of alumina, synthetic magnesite, silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide, magnesium oxide, talc, mica and hydrotalcite. Preferably there is.

  The filler (D) is more preferably at least one selected from the group consisting of alumina, synthetic magnesite, crystalline silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide and magnesium oxide, More preferably, it is at least one selected from the group consisting of alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide and magnesium oxide. By using these preferable fillers, the heat dissipation of the cured product can be further enhanced.

  The filler (D) is more preferably at least one selected from the group consisting of spherical alumina, crushed alumina and spherical aluminum nitride, and more preferably spherical alumina or spherical aluminum nitride. By using these preferable fillers, the heat dissipation of the cured product can be further enhanced.

  The new Mohs hardness of the filler (D) is preferably 3.1 or higher, more preferably 4 or higher, preferably 14 or lower, more preferably 9 or lower, still more preferably 7 or lower. When the new Mohs hardness of the filler (D) is not less than the above lower limit, the thermal conductivity and workability of the cured product of the resin sheet can be achieved at a high level. When the new Mohs hardness of the filler (D) is not more than the above upper limit, it is easy to achieve both high thermal conductivity and high workability of the cured product.

  From the viewpoint of considerably reducing the elastic modulus of the cured product, the new Mohs hardness of the filler (D) is preferably 9 or less, and particularly preferably 7 or less.

  Since the new Mohs hardness is 7 or less, the filler (D) is preferably at least one selected from the group consisting of synthetic magnesite, crystalline silica, zinc oxide and magnesium oxide.

  The filler (D) may be a spherical filler or a crushed filler. The filler (D) is particularly preferably spherical. In the case of a spherical filler, since it can be filled with high density, the heat dissipation of the cured product can be further enhanced.

  Examples of the crushed filler include crushed alumina. The crushed filler can be obtained, for example, by crushing a massive inorganic substance using a uniaxial crusher, a biaxial crusher, a hammer crusher, a ball mill, or the like. By using the crushed filler, the resin composition and the filler in the resin sheet are likely to be bridged or have a structure in which they are close to each other efficiently. Therefore, the thermal conductivity of the cured product can be further enhanced. Moreover, the crushed filler is generally cheaper than a normal filler. For this reason, the cost of a resin composition and a resin sheet can be reduced by use of the crushed filler.

  The average particle size of the crushed filler is preferably 12 μm or less. When the average particle diameter exceeds 12 μm, the crushed filler cannot be dispersed with high density in the resin sheet, and the dielectric breakdown characteristics of the cured product of the resin sheet may deteriorate. The average particle size of the crushed filler is more preferably 10 μm or less, and preferably 1 μm or more. If the average particle size of the crushed filler is too small, it may be difficult to fill the crushed filler with high density.

  The aspect ratio of the crushed filler is not particularly limited. The aspect ratio of the crushed filler is preferably 1.5 or more and 20 or less. Fillers with an aspect ratio of less than 1.5 are relatively expensive. Therefore, the cost of the resin sheet increases. When the aspect ratio is 20 or less, filling of the crushed filler is easy.

  The aspect ratio of the crushed filler can be determined, for example, by measuring the crushed surface of the filler using a digital image analysis type particle size distribution measuring device (trade name: FPA, manufactured by Nippon Luft).

  When the filler (D) is a spherical filler, the average particle diameter of the spherical filler is preferably 0.1 μm or more and 40 μm or less. When the average particle size is 0.1 μm or more, the filler (D) can be easily filled at a high density. When the average particle size is 40 μm or less, the dielectric breakdown characteristics of the cured product are 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.

  In 100% by volume of the resin sheet and 100% by volume of the resin composition, the content of the filler (D) is preferably 20% by volume or more and 90% by volume or less, respectively. When the content of the filler (D) is within the above range, the heat dissipation property of the cured product is further enhanced, and the handling property of the resin sheet is further improved. From the viewpoint of further increasing the heat dissipation of the cured product, the content of the filler (D) in 100% by volume of the resin sheet and 100% by volume of the resin composition is more preferably 30% by volume or more, and further preferably 35% by volume. % Or more, more preferably 85% by volume or less, still more preferably 80% by volume or less, particularly preferably 70% by volume or less, and most preferably 60% by volume or less. When the content of the filler (D) is not less than the above lower limit, the heat dissipation of the cured product is further enhanced. When the content of the filler (D) is not more than the above upper limit, the handling property of the resin sheet is further enhanced, and the storage stability of the resin composition is further enhanced.

(First silane coupling agent (E1) and second silane coupling agent (E2))
The resin composition according to the present invention and the resin sheet according to the present invention are respectively a first silane coupling agent (E1) having an epoxy group and a second silane coupling agent having an alkyl group having 4 to 12 carbon atoms. (E2). By using the first and second silane coupling agents (E1) and (E2) in combination, the water resistance and moisture resistance of the cured product of the resin composition and the resin sheet, and the adhesion target member of the resin composition and the resin sheet Adhesiveness to is considerably increased. Further, by using the first and second silane coupling agents (E1) and (E2), aggregation of the filler (D) can be suppressed, and the thermal conductivity and dielectric breakdown characteristics of the cured product can be further enhanced. .

  The first silane coupling agent (E1) is different from the epoxy compound (B1). Examples of the first silane coupling agent (E1) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and the like. You may use the silane coupling agent which has an epoxy group other than these. As for the 1st silane coupling agent (E1), only 1 type may be used and 2 or more types may be used together.

  The second silane coupling agent (E2) is a silane coupling agent having an alkyl group having 4 to 12 carbon atoms. The second silane coupling agent (E2) is preferably different from the first silane coupling agent (E1). The alkyl group having 4 to 12 carbon atoms may be linear or may have a branched structure. Examples of the alkyl group having 4 to 12 carbon atoms include n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t- Examples thereof include a butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, an isohexyl group, and a 2-ethylhexyl group. The alkyl group having 4 to 12 carbon atoms in the second silane coupling agent (E2) preferably has 4 to 12 carbon atoms in the linear portion of the alkyl group. For example, the carbon number of the 2-ethylhexyl group is 8, and the carbon number of the straight chain portion is 6. The second silane coupling agent (E2) preferably has a linear alkyl group having 4 to 12 carbon atoms.

  From the viewpoint of further improving the water resistance and moisture resistance of the cured product, the second silane coupling agent (E2) preferably has an alkyl group having 5 or more carbon atoms, more preferably an alkyl having 6 or more carbon atoms. A group, preferably an alkyl group having 10 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms. From the viewpoint of further increasing the water resistance and moisture resistance of the cured product, the second silane coupling agent (E2) preferably has a linear alkyl group having 6 to 10 carbon atoms.

  Specific examples of the second silane coupling agent (E2) include n-butyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, and n-octyltrimethoxysilane. , N-decyltrimethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, sec-butyltrimethoxysilane, t-butyltrimethoxysilane, isopentyltrimethoxysilane, neopentyltrimethoxysilane, t-pentyltrimethoxysilane , Isohexyltrimethoxysilane, 2-ethylhexyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxysilane, n-heptyltriethoxysilane, n-octyl Rutriethoxysilane, isopropyltriethoxysilane, isobutyltriethoxysilane, sec-butyltriethoxysilane, t-butyltriethoxysilane, isopentyltriethoxysilane, neopentyltriethoxysilane, t-pentyltriethoxysilane, isohexyl Examples include triethoxysilane and 2-ethylhexyltriethoxysilane. You may use the silane coupling agent which has a C4-C12 alkyl group other than these. As for a 2nd silane coupling agent (E2), only 1 type may be used and 2 or more types may be used together.

  In the resin sheet according to the present invention, the total content of the first silane coupling agent (E1) and the second silane coupling agent (E2) in the total 100% by weight of all the resin components X is 0.00. It is preferable that it is 01 weight% or more and 20 weight% or less. The total content of the first and second silane coupling agents (E1) and (E2) in the total 100% by weight of the total resin component X in the resin sheet is more preferably 0.05% by weight or more, and more preferably Is 10% by weight or less. When the total content of the first and second silane coupling agents (E1) and (E2) is not less than the above lower limit, the insulating properties of the cured product of the resin sheet, water resistance and moisture resistance, and adhesiveness are obtained. It gets even higher. When the total content of the first and second silane coupling agents (E1) and (E2) is not more than the above upper limit, the heat resistance of the cured product of the resin sheet is further enhanced. Furthermore, when the total content of the first and second silane coupling agents (E1) and (E2) is not less than the above lower limit and not more than the above upper limit, the aggregation of the filler (D) can be further suppressed and cured. The thermal conductivity, dielectric breakdown characteristics, water resistance, moisture resistance and adhesion of the object can be further enhanced.

  In the resin composition according to the present invention, the total content of the first silane coupling agent (E1) and the second silane coupling agent (E2) is 0 in 100% by weight of the total resin component X. It is preferably 0.05% by weight or more and 20% by weight or less. The total content of the first and second silane coupling agents (E1) and (E2) in the total 100% by weight of the total resin component X in the resin composition is more preferably 0.1% by weight or more. Preferably it is 15 weight% or less. When the total content of the first and second silane coupling agents (E1) and (E2) is not less than the above lower limit, the insulation of the cured product of the resin composition, water resistance and moisture resistance, and adhesiveness Becomes even higher. When the total content of the first and second silane coupling agents (E1) and (E2) is not more than the above upper limit, the heat resistance of the cured product of the resin composition is further enhanced.

  In the resin sheet according to the present invention and the resin composition according to the present invention, the weight ratio of the first silane coupling agent (E1) and the second silane coupling agent (E2) is 99: 1 to 1. : 99, preferably 90:10 to 10:90, more preferably 80:20 to 20:80. When the content of the first silane coupling agent (E1) is relatively increased, the adhesiveness of the cured product is further improved. When the content of the second silane coupling agent (E2) is relatively increased, the water resistance and moisture resistance of the cured product are further improved.

(Other ingredients)
The resin composition and resin sheet according to the present invention may contain rubber particles. By using the rubber particles, the stress relaxation property and flexibility of the resin sheet, the cured product of the resin composition, and the cured product of the resin sheet can be enhanced.

  The resin composition and resin sheet according to the present invention may contain a dispersant. Use of the dispersant can further enhance the thermal conductivity and dielectric breakdown characteristics of the cured product.

  The dispersant preferably has a functional group containing a hydrogen atom having hydrogen bonding properties. When the dispersing agent has a functional group containing a hydrogen atom having hydrogen bonding properties, the thermal conductivity and dielectric breakdown characteristics of the cured product can be further enhanced. Examples of the functional group containing a hydrogen atom having hydrogen bonding include a carboxyl group (pKa = 4), a phosphoric acid group (pKa = 7), a phenol group (pKa = 10), and the like.

  The pKa of the functional group containing a hydrogen atom having hydrogen bonding property is preferably 2 or more, more preferably 3 or more, preferably 10 or less, more preferably 9 or less. When the pKa of the functional group is not less than the lower limit, the acidity of the dispersant does not become too high. Therefore, the storage stability of the resin composition and the resin sheet is further enhanced. When the pKa of the functional group is not more than the above upper limit, the function as the dispersant is sufficiently fulfilled, and the thermal conductivity and dielectric breakdown characteristics of the cured product are further enhanced.

  The functional group containing a hydrogen atom having hydrogen bonding properties is preferably a carboxyl group or a phosphate group. In this case, the thermal conductivity and dielectric breakdown characteristics of the cured product are further enhanced.

  Specific examples of the dispersant include a polyester carboxylic acid, a polyether carboxylic acid, a polyacrylic carboxylic acid, an aliphatic carboxylic acid, a polysiloxane carboxylic acid, a polyester phosphoric acid, and a polyether type. Examples thereof include phosphoric acid, polyacrylic phosphoric acid, aliphatic phosphoric acid, polysiloxane phosphoric acid, polyester phenol, polyether phenol, polyacrylic phenol, aliphatic phenol, and polysiloxane phenol. As for the said dispersing agent, only 1 type may be used and 2 or more types may be used together.

  In 100% by weight of the resin composition and 100% by weight of the resin sheet, the content of the dispersant is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 20% by weight or less. More preferably, it is 10% by weight or less. When the content of the dispersant is not less than the above lower limit and not more than the upper limit, aggregation of the filler (D) can be suppressed, and the heat dissipation and dielectric breakdown characteristics of the cured product can be further enhanced.

  In order to further improve the handling properties, the resin sheet according to the present invention may contain a base material such as glass cloth, glass nonwoven fabric, and aramid nonwoven fabric. However, even if the base material is not included, the resin sheet has a self-supporting property at room temperature (23 ° C.) and an excellent handling property. Therefore, it is preferable that the resin sheet does not include a base material, and particularly it does not include glass cloth. When the resin sheet does not contain the base material, the thickness of the resin sheet can be reduced, and the thermal conductivity of the cured product can be further enhanced. Furthermore, when the resin sheet does not contain the above-mentioned base material, various processes such as laser processing or drilling can be easily performed on the resin sheet as necessary. In addition, self-supporting means that the shape of a sheet can be maintained and handled as a sheet even if there is no support such as a PET film or copper foil.

  Furthermore, the resin composition and the resin sheet according to the present invention may contain a tackifier, a plasticizer, a thixotropic agent, a flame retardant, a photosensitizer, a colorant, and the like as necessary.

  Each of the resin composition and the resin sheet according to the present invention preferably contains no solvent or contains a solvent at 5% by weight or less. In 100% by weight of the resin composition and the resin sheet according to the present invention, the content of the solvent is more preferably 1% by weight or less, still more preferably 0.5% by weight or less. Most preferably, the resin composition and the resin sheet according to the present invention do not contain a solvent, respectively. When the content of the solvent is small, a drying step is not required to remove the solvent, or the amount of heat necessary for drying can be reduced. If the content of the solvent is small, the volatilization amount of the solvent at the time of curing decreases, and the environmental load can be reduced. Furthermore, the handleability of a resin composition and a resin sheet becomes high.

(Resin composition and resin sheet)
Each of the resin composition and the resin sheet according to the present invention is used for bonding a heat conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer.

  The method for producing the resin composition according to the present invention is not particularly limited. The resin composition according to the present invention can be obtained, for example, by mixing the materials described above.

  The method for producing the resin sheet according to the present invention is not particularly limited. The resin sheet can be obtained, for example, by forming a mixture of the above-described materials into a sheet shape by a method such as a solvent casting method or an extrusion film forming method. Defoaming is preferred when forming into a sheet.

  The thickness of the resin sheet is not particularly limited. The thickness of the resin sheet is preferably 10 μm or more, more preferably 50 μm or more, further preferably 70 μm or more, preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 120 μm or less. When the thickness is not less than the above lower limit, the insulating property of the cured product of the resin sheet is increased. When the thickness is less than or equal to the above upper limit, heat dissipation becomes high when the heat conductor is bonded to the conductive layer.

  It is preferable that the glass transition temperature Tg of the resin composition and resin sheet in an uncured state is 25 ° C. or less, respectively. When the glass transition temperature is 25 ° C. or lower, the resin sheet is hard and hardly brittle at room temperature. For this reason, the handleability of the resin sheet in an uncured state is enhanced.

  The thermal conductivity of the cured product of the resin composition and the resin sheet is preferably 0.7 W / m · K or more, more preferably 1.0 W / m · K or more, and further preferably 1.5 W / m · K or more. is there. When the thermal conductivity is at least the above lower limit, the heat dissipation of the cured product is sufficiently high.

  The dielectric breakdown voltage of the cured product of the resin composition and the resin sheet is preferably 30 kV / mm or more, more preferably 40 kV / mm or more, further preferably 50 kV / mm or more, particularly preferably 80 kV / mm or more, and most preferably 100 kV. / Mm or more. If the dielectric breakdown voltage is too low, the insulating properties may be lowered when the resin composition and the resin sheet are used for a large current application such as for power devices.

  The resin composition according to the present invention can be applied using screen printing, a dispenser, a spin coater or the like. The resin composition according to the present invention is preferably used for screen printing. The resin composition according to the present invention is preferably a screen printing resin composition.

(Laminated structure)
The resin sheet according to the present invention constitutes an insulating layer of a laminated structure in which a conductive layer is laminated via an insulating layer on at least one surface of a thermal conductor having a thermal conductivity of 10 W / m · K or more. Is preferably used.

  In FIG. 1, an example of the laminated structure using the resin composition or resin sheet which concerns on one Embodiment of this invention is shown.

  The laminated structure 1 shown in FIG. 1 is opposite to the heat conductor 2, the insulating layer 3 laminated on one surface 2a of the heat conductor 2, and the surface of the insulating layer 3 on which the heat conductor 2 is laminated. And a conductive layer 4 laminated on the other surface of the side. The insulating layer 3 is formed by curing the resin sheet according to the present invention. The heat conductivity of the heat conductor 2 is 10 W / m · K or more.

  It is only necessary that the insulating layer 3 and the conductive layer 4 are laminated in this order on at least one surface 2a of the heat conductor 2, and the insulating layer and the conductive layer are also formed on the other surface 2b of the heat conductor 2. You may laminate | stack in order.

  In the laminated structure 1, since the insulating layer 3 has a high thermal conductivity, heat from the conductive layer 4 side is easily transmitted to the thermal conductor 2 through the insulating layer 3. In the laminated structure 1, heat can be efficiently dissipated by the heat conductor 2.

  For example, after bonding a metal body to each conductive layer such as a laminated board or multilayer wiring board provided with copper circuits on both sides, copper foil, copper plate, semiconductor element or semiconductor package via a resin composition or resin sheet, The laminated structure 1 can be obtained by curing the resin composition or the resin sheet.

  The heat conductor whose heat conductivity is 10 W / m · K or more is not particularly limited. Examples of the heat conductor having a thermal conductivity of 10 W / m · K or more include aluminum, copper, alumina, beryllia, silicon carbide, silicon nitride, aluminum nitride, and graphite sheet. Especially, it is preferable that the heat conductor whose said heat conductivity is 10 W / m * K or more is copper or aluminum. Copper or aluminum is excellent in heat dissipation.

  The resin composition or resin sheet according to the present invention is suitable for bonding a thermal conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer of a semiconductor device in which a semiconductor element is mounted on a substrate. Used for.

  The resin composition or resin sheet according to the present invention is a thermal conductor having a thermal conductivity of 10 W / m · K or more in a conductive layer of an electronic component device in which an electronic component element other than a semiconductor element is mounted on a substrate. Is also preferably used for bonding.

  When the semiconductor element is a power device element for a large current, the cured product of the resin sheet is required to be more excellent in insulation or heat resistance. Therefore, the resin composition or resin sheet according to the present invention is suitably used for such applications.

  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.

  The following materials were prepared.

[Polymer (A)]
(1) Bisphenol A type phenoxy resin (trade name: E1256, Mw = 51000, Tg = 98 ° C., manufactured by Japan Epoxy Resin Co., Ltd.)
(2) High heat resistance phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: FX-293, Mw = 43700, Tg = 163 ° C.)
(3) Epoxy group-containing styrene resin (manufactured by NOF Corporation, trade name: Marproof G-1010S, Mw = 100000, Tg = 93 ° C.)

[Epoxy compound having epoxy group (B1)]
(1) Bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828US, Mw = 370)
(2) Bisphenol F type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 806L, Mw = 370)
(3) Trifunctional glycidyldiamine type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 630, Mw = 300)
(4) Fluorene skeleton epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: ONCOAT EX1011, Mw = 486)
(5) Naphthalene skeleton liquid epoxy resin (manufactured by DIC, trade name: EPICLON HP-4032D, Mw = 304)
(6) Hexahydrophthalic acid skeleton liquid epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: AK-601, Mw = 284)
(7) Bisphenol A type solid epoxy resin (product name: 1003, Mw = 1300, manufactured by Japan Epoxy Resin Co., Ltd.)

[Oxetane compound having oxetane group (B2)]
(1) Oxetane resin containing benzene skeleton (manufactured by Ube Industries, trade name: etanacol OXTP, Mw = 362.4)

[Curing agent (C)]
(1) Alicyclic skeleton acid anhydride (manufactured by Shin Nippon Chemical Co., Ltd., trade name: MH-700)
(2) Aromatic skeleton acid anhydride (manufactured by Sartomer Japan, trade name: SMA resin EF60)
(3) Polyalicyclic skeleton acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: HNA-100)
(4) Terpene-based skeleton acid anhydride (manufactured by Japan Epoxy Resin, trade name: Epicure YH-306)
(5) Biphenyl skeleton phenolic resin (Madewa Kasei Co., Ltd., trade name: MEH-7851-S)
(6) Allyl group-containing skeletal phenol resin (manufactured by Japan Epoxy Resin, trade name: YLH-903)
(7) Triazine skeleton phenolic resin (manufactured by DIC, trade name: Phenolite KA-7052-L2)
(8) Melamine skeleton phenolic resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name: PS-6492)
(9) Dicyandiamide

[Filler (D)]
(1) 5 μm crushed alumina (crushed filler, manufactured by Nippon Light Metal Co., Ltd., trade name: LT300C, average particle diameter 5 μm, maximum particle diameter 15 μm, thermal conductivity 36 W / m · K, new Mohs hardness 12)
(2) 2 μm crushed alumina (crushed filler, manufactured by Nippon Light Metal Co., Ltd., trade name: LS-242C, average particle diameter 2 μm, maximum particle diameter 20 μm, thermal conductivity 36 W / m · K, new Mohs hardness 12)
(3) 6 μm fractured aluminum nitride (crushed filler, manufactured by Toyo Aluminum Co., Ltd., trade name: FLC, average particle diameter 6 μm, maximum particle diameter 20 μm, thermal conductivity 200 W / m · K, new Mohs hardness 11)
(4) Spherical alumina (Denka Co., Ltd., trade name: DAM-10, average particle size 10 μm, maximum particle size 30 μm, thermal conductivity 36 W / m · K, new Mohs hardness 12)
(5) Synthetic magnesite (Kamishima Chemical Co., Ltd., trade name: MSL, average particle size 6 μm, maximum particle size 20 μm, thermal conductivity 15 W / m · K, new Mohs hardness 3.5)
(6) Aluminum nitride (manufactured by Toyo Aluminum Co., Ltd., trade name: TOYALNITE-FLX, average particle diameter 14 μm, maximum particle diameter 30 μm, thermal conductivity 200 W / m · K, new Mohs hardness 11)
(7) Crystalline silica (manufactured by Tatsumori Co., Ltd., trade name: Crystallite CMC-12, average particle size 5 μm, maximum particle size 20 μm, thermal conductivity 10 W / m · K, new Mohs hardness 7)
(8) Silicon carbide (manufactured by Shinano Denki Smelting Co., Ltd., trade name: Shinano Random GP # 700, average particle diameter 17 μm, maximum particle diameter 70 μm, thermal conductivity 125 W / m · K, new Mohs hardness 13)
(9) Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., trade name: LPZINC-5, average particle size 5 μm, maximum particle size 20 μm, thermal conductivity 54 W / m · K, new Mohs hardness 5)
(10) Magnesium oxide (manufactured by Sakai Chemical Industry Co., Ltd., trade name: SMO Large Particle, average particle size 1.1 μm, maximum particle size 7 μm, thermal conductivity 35 W / m · K, new Mohs hardness 6)
(11) Mica (manufactured by Yamaguchi Mica Industry Co., Ltd., trade name: SJ005, average particle diameter 5 μm, new Mohs hardness 2.7)
(12) Talc (manufactured by Nippon Talc Co., Ltd., trade name: K-1, average particle size 8 μm, new Mohs hardness 1)

[First silane coupling agent (E1)]
(1) Epoxysilane coupling agent 1 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE403)
(2) Epoxysilane coupling agent 2 (Shin-Etsu Chemical Co., Ltd., trade name: KBM303)
(3) Epoxysilane coupling agent 3 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403)

[Second silane coupling agent (E2)]
(1) Hexylsilane coupling agent (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: hexyltrimethoxysilane having an n-hexyl group having 6 carbon atoms)
(2) Octylsilane coupling agent (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: n-octyltriethoxysilane having an n-octyl group having 8 carbon atoms)
(3) Decylsilane coupling agent (having an n-decyl group having 10 carbon atoms, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM3103-C)

[Silane coupling agents other than the first and second silane coupling agents (E1) and (E2)]
(1) Aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM903)
(2) Mercaptosilane coupling agent (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: (3-mercaptopropyl) triethoxysilane)

[Dispersant]
(1) Acrylic dispersant (manufactured by Big Chemie Japan, trade name: Disperbyk-2070, pKa has a carboxyl group of 4)
(2) Polyether-based dispersant (manufactured by Enomoto Kasei Co., Ltd., trade name: ED151, pKa has 7 phosphate groups)

[solvent]
Methyl ethyl ketone

(Examples 1-31 and Comparative Examples 1-7)
Using a homodisper type stirrer, each raw material was blended and kneaded in the proportions shown in Tables 1 to 5 below (the blending unit is parts by weight) to prepare a resin composition that is an insulating material.

(Examples 32-64 and Comparative Examples 8-14)
Using a homodisper type stirrer, each raw material was blended in the proportions shown in Tables 6 to 10 below (the blending unit is parts by weight) and kneaded to prepare an insulating composition.

  The insulating composition was applied to a release PET sheet having a thickness of 50 μm so as to have a thickness of 100 μm, and dried in an oven at 90 ° C. for 30 minutes to produce a resin sheet as an insulating material on the PET sheet. .

(Evaluation)
(1-1) Coating property of uncured resin composition The coating property when coating is performed on a PET sheet using an applicator at room temperature (23 ° C) using the resin composition based on the following criteria. evaluated.

[Criteria for coating properties]
◯: The resin composition has good fluidity and can be easily applied. Δ: Although the resin composition can be applied, streaks or unevenness due to filler aggregation occurs. ×: The resin composition cannot be applied.

(1-2) Handling property of uncured resin sheet A laminate sheet having a PET sheet and a resin sheet formed on the PET sheet was cut into a size of 460 mm × 610 mm to obtain a test sample. Using the obtained test sample, the handling property when the resin sheet before thermosetting was peeled from the PET sheet at room temperature (23 ° C.) was evaluated according to the following criteria.

[Handling criteria]
○: The resin sheet is not deformed and can be easily peeled. Δ: Although the resin sheet can be peeled, the sheet is stretched or broken. ×: The resin sheet cannot be peeled.

(2) Glass transition temperature Using a differential scanning calorimeter “DSC220C” (manufactured by Seiko Instruments Inc.), a resin composition in an uncured state and a resin sheet in an uncured state at a heating rate of 3 ° C./min. The glass transition temperature of was measured.

(3) Thermal conductivity The thermal conductivity of the hardened | cured material of a resin composition and the resin sheet was measured using the heat conductivity meter "rapid thermal conductivity meter QTM-500" by Kyoto Electronics Industry Co., Ltd.

  In addition, the cured product of the resin composition used for the measurement of thermal conductivity was coated on the release PET sheet having a thickness of 50 μm so that the resin composition had a thickness of 100 μm, and then 1 ° C. at 120 ° C. The resin composition was cured for 1 hour at 200 ° C. for 1 hour.

(4) Water resistance A resin composition (thickness 100 μm) or a resin sheet is sandwiched between an aluminum plate having a thickness of 1.5 mm and an electrolytic copper foil having a thickness of 35 μm, and maintained at 120 ° C. while maintaining a pressure of 4 MPa with a vacuum press. The resin composition or resin sheet was press-cured for 1 hour and further at 200 ° C. for 1 hour to form a copper-clad laminate. The obtained copper-clad laminate was cut into a size of 100 mm × 100 mm, and the copper foil was peeled off to obtain a test sample. After immersing the obtained test sample in a boiling bath for 24 hours, water resistance was evaluated by the presence or absence of occurrence of swelling or peeling of the cured product from the aluminum plate. Water resistance was determined according to the following criteria.

[Criteria for water resistance]
○: After 24 hours, no change ○: After 24 hours, there are bulges of 1 mm or less at the four corners △: After 24 hours, there are bulges of 1 mm or less over the entire surface. Yes

(5) Moisture resistance A resin composition (thickness: 100 μm) or a resin sheet is sandwiched between an aluminum plate with a thickness of 1.5 mm and an electrolytic copper foil with a thickness of 35 μm, and at 120 ° C. while maintaining a pressure of 4 MPa with a vacuum press. The resin composition or resin sheet was press-cured for 1 hour and further at 200 ° C. for 1 hour to form a copper-clad laminate. The obtained copper-clad laminate was cut into a size of 100 mm × 100 mm, and the copper foil was peeled off to obtain a test sample. The obtained test sample was allowed to stand in an autoclave at 121 ° C., 2 atm and 100% relative humidity for 24 hours, and then the moisture resistance was evaluated by the presence or absence of occurrence of blistering or peeling of the cured product from the aluminum plate. The moisture resistance was determined according to the following criteria.

[Criteria for moisture resistance]
○: After 24 hours, no change ○: After 24 hours, there are bulges of 1 mm or less at the four corners △: After 24 hours, there are bulges of 1 mm or less over the entire surface. Yes

(6) Solder heat resistance test (heat resistance)
A resin composition (thickness: 100 μm) or a resin sheet is sandwiched between an aluminum plate having a thickness of 1.5 mm and an electrolytic copper foil having a thickness of 35 μm, and maintained at a pressure of 4 MPa with a vacuum press machine at 120 ° C. for 1 hour, and further 200 The resin composition or resin sheet was press-cured at 1 ° C. for 1 hour to form a copper-clad laminate. The obtained copper-clad laminate was cut into a size of 50 mm × 60 mm to obtain a test sample. The obtained test sample was floated in a solder bath at 288 ° C. with the copper foil side facing down, and the time until the copper foil swelled or peeled off was measured and judged according to the following criteria.

[Criteria for solder heat resistance test]
○○: No swelling or peeling even after 10 minutes ○: Swelling or peeling occurs after 3 minutes and before 10 minutes △: Swelling after 1 minute and before 3 minutes or Peeling occurs ×: Swelling or peeling occurs before 1 minute elapses

(7) Dielectric breakdown voltage (withstand voltage)
The resin composition was coated on a release PET sheet having a thickness of 50 μm so as to have a thickness of 100 μm, and then the resin composition was cured at 120 ° C. for 1 hour and then at 200 ° C. for 1 hour to obtain a resin. A test sample using the composition was prepared.

  Moreover, the resin sheet was cut out to a size of 100 mm × 100 mm and cured at 120 ° C. for 1 hour and then at 200 ° C. for 1 hour to obtain a test sample using the resin sheet.

  Using a withstand voltage tester (MODEL7473, manufactured by EXTECH Electronics), an AC voltage was applied between test samples (cured resin composition or cured resin sheet) at a rate of 1 kV / sec. Applied. The voltage at which the cured product of the resin composition or resin sheet was destroyed was taken as the dielectric breakdown voltage.

(8) Adhesive strength (adhesiveness)
A resin composition (thickness: 100 μm) or a resin sheet is sandwiched between an aluminum plate having a thickness of 1.5 mm and an electrolytic copper foil having a thickness of 35 μm, and maintained at a pressure of 4 MPa with a vacuum press machine at 120 ° C. for 1 hour, and further 200 The resin composition or resin sheet was press-cured at 1 ° C. for 1 hour to form a copper-clad laminate. The copper foil of the obtained copper-clad laminate was etched to form a 10 mm wide copper foil strip to obtain a test sample.

  Peel strength when copper foil is peeled off at an angle of 90 ° C with respect to an aluminum plate at a pulling speed of 50 mm / min using a tensile tester (manufactured by A & D Corp., universal testing machine Tensilon RTF) And the obtained measured value was defined as the adhesive strength of the resin composition or resin sheet.

  The results are shown in Tables 1 to 10 below. In Tables 1 to 10 below, * 1 indicates “content in 100% by weight of all resin components X (% by weight)”. * 2 indicates “content in 100% by volume of resin composition or 100% by volume of resin sheet (volume%)”.

DESCRIPTION OF SYMBOLS 1 ... Laminated structure 2 ... Thermal conductor 2a ... 1st surface 2b ... 2nd surface 3 ... Insulating layer 4 ... Conductive layer

Claims (20)

A paste-like resin composition used for bonding a heat conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer,
A curable compound having an epoxy group or an oxetane group;
A curing agent;
A filler,
A first silane coupling agent having an epoxy group;
And a second silane coupling agent having an alkyl group having 4 to 12 carbon atoms.   The resin composition according to claim 1, wherein the second silane coupling agent has a linear alkyl group having 6 to 10 carbon atoms.   The filler according to claim 1 or 2, wherein the filler is at least one selected from the group consisting of alumina, synthetic magnesite, crystalline silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide, and magnesium oxide. The resin composition as described.   The curable compound has an aromatic skeleton and an epoxy group, and has an epoxy monomer having a weight average molecular weight of 600 or less, or has an aromatic skeleton and an oxetane group, and has a weight average molecular weight of 600 or less. The resin composition of any one of Claims 1-3 containing an oxetane monomer.   The said hardening | curing agent is a phenol resin, dicyandiamide, or an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. 2. The resin composition according to item 1.   Fat obtained by adding the curing agent as an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or a terpene compound and maleic anhydride The resin composition according to claim 5, which is an acid anhydride having a cyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. The resin composition according to claim 6, wherein the curing agent is an acid anhydride represented by any of the following formulas (1) to (4).
In said formula (4), R1 and R2 show hydrogen, a C1-C5 alkyl group, or a hydroxyl group, respectively. A resin sheet used for bonding a heat conductor having a thermal conductivity of 10 W / m · K or more to a conductive layer,
A polymer having a weight average molecular weight of 10,000 or more;
A curable compound having a weight average molecular weight of less than 10,000 and having an epoxy group or an oxetane group;
A curing agent;
A filler,
A first silane coupling agent having an epoxy group;
The resin sheet containing the 2nd silane coupling agent which has a C4-C12 alkyl group.   The resin sheet according to claim 8, wherein the second silane coupling agent has a linear alkyl group having 6 to 10 carbon atoms.   10. The filler according to claim 8 or 9, wherein the filler is at least one selected from the group consisting of alumina, synthetic magnesite, crystalline silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide and magnesium oxide. The resin sheet of description.   The resin sheet according to any one of claims 8 to 10, wherein the polymer has an aromatic skeleton and has a weight average molecular weight of 30,000 or more.   The curable compound has an aromatic skeleton and an epoxy group, and has an epoxy monomer having a weight average molecular weight of 600 or less, or has an aromatic skeleton and an oxetane group, and has a weight average molecular weight of 600 or less. The resin sheet according to any one of claims 8 to 11, comprising an oxetane monomer.   Content of the polymer in a total of 100% by weight of resin components in the resin sheet containing the polymer, the curable compound, the curing agent, the first silane coupling agent, and the second silane coupling agent. The resin sheet according to any one of claims 8 to 12, wherein the content of the curable compound is 20 wt% or more and 60 wt% or less, and the content of the curable compound is 10 wt% or more and 60 wt% or less.   The resin sheet according to claim 8, wherein the polymer is a phenoxy resin.   The said hardening | curing agent is a phenol resin, dicyandiamide, or an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. The resin sheet according to claim 1.   Fat obtained by adding the curing agent as an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or a terpene compound and maleic anhydride The resin sheet according to claim 15, which is an acid anhydride having a cyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. The resin sheet according to claim 16, wherein the curing agent is an acid anhydride represented by any of the following formulas (1) to (4).
In said formula (4), R1 and R2 show hydrogen, a C1-C5 alkyl group, or a hydroxyl group, respectively. A thermal conductor having a thermal conductivity of 10 W / m · K or more;
An insulating layer laminated on at least one surface of the thermal conductor;
A conductive layer laminated on a surface opposite to the surface on which the thermal conductor of the insulating layer is laminated,
The laminated structure in which the said insulating layer is formed by hardening the resin composition of any one of Claims 1-7. A thermal conductor having a thermal conductivity of 10 W / m · K or more;
An insulating layer laminated on at least one surface of the thermal conductor;
A conductive layer laminated on a surface opposite to the surface on which the thermal conductor of the insulating layer is laminated,
The laminated structure in which the said insulating layer is formed by hardening the resin sheet of any one of Claims 8-17.   The laminated structure according to claim 18 or 19, wherein the heat conductor is a metal.