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WO2012073360A1 - Feuille isolante et structure stratifiée - Google Patents

Feuille isolante et structure stratifiée Download PDF

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Publication number
WO2012073360A1
WO2012073360A1 PCT/JP2010/071540 JP2010071540W WO2012073360A1 WO 2012073360 A1 WO2012073360 A1 WO 2012073360A1 JP 2010071540 W JP2010071540 W JP 2010071540W WO 2012073360 A1 WO2012073360 A1 WO 2012073360A1
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WO
WIPO (PCT)
Prior art keywords
insulating sheet
weight
sheet according
inorganic filler
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/071540
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English (en)
Japanese (ja)
Inventor
前中　寛
康成 日下
卓司 青山
高橋　良輔
峻右 近藤
孝徳 井上
貴志 渡邉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP2010547778A priority Critical patent/JPWO2012073360A1/ja
Priority to PCT/JP2010/071540 priority patent/WO2012073360A1/fr
Publication of WO2012073360A1 publication Critical patent/WO2012073360A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
    • H05K1/0203—Cooling of mounted components
    • H05K1/0209—External configuration of printed circuit board adapted for heat dissipation, e.g. lay-out of conductors, coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the present invention relates to an insulating sheet used for adhering a thermal conductor having a thermal conductivity of 10 W / m ⁇ K or more to a conductive layer, and more specifically, handling property and storage stability in an uncured state.
  • the present invention relates to an insulating sheet that is high and has high adhesiveness and heat dissipation of a cured product after curing, and a laminated structure using the insulating sheet.
  • insulating layer is formed using a paste-like or sheet-like insulating adhesive material.
  • 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.
  • Patent Document 2 An insulating adhesive material that does not contain glass cloth is also known.
  • the example of Patent Document 2 below includes an insulating adhesive containing bisphenol A type epoxy resin, phenoxy resin, phenol novolac, 1-cyanoethyl-2-phenylimidazole, ⁇ -glycidoxypropyltrimethoxysilane, and alumina.
  • Agents are disclosed.
  • examples of the epoxy resin curing agent include tertiary amines, acid anhydrides, imidazole compounds, polyphenol resins, and mask isocyanates.
  • a glass cloth is used in order to improve handling properties.
  • 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.
  • cured material of the insulation adhesive sheet containing a glass cloth is comparatively low, sufficient heat dissipation may not be obtained.
  • special impregnation equipment must be prepared for impregnating the glass cloth with the adhesive composition.
  • the downsizing and high performance of electrical equipment are progressing.
  • the printed wiring board used for the said electronic device and communication apparatus multilayering and a thin film are progressing, and the mounting density of an electronic component is high.
  • a large amount of heat is easily generated from the electronic components, and the need to dissipate the generated heat is increasing.
  • the insulating layer of the printed wiring board needs to have high thermal conductivity.
  • a large amount of filler having high thermal conductivity with a thermal conductivity of 10 W / m ⁇ K or more is added to the insulating adhesive material for forming the insulating layer.
  • a filling method is generally employed.
  • the adhesiveness of the insulating layer tends to be low.
  • the adhesive of the above-mentioned insulating adhesive material containing a large amount of filler is likely to be lowered and peeled off, particularly in applications where a member to be bonded provided with a fine wiring pattern is bonded for miniaturization and high performance. There is a problem that it is easy.
  • a method of blending a filler such as alumina having high thermal conductivity with a thermal conductivity of 10 W / m ⁇ K or more is used in the insulating adhesive material.
  • Alumina is also used in the insulating adhesive described in Patent Document 2.
  • the workability of the cured product of the insulating adhesive material containing alumina may be low.
  • the 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 can improve handling and storage stability in an uncured state, Furthermore, it is providing the insulating sheet which can make high heat dissipation of the hardened
  • a limited object of the present invention is to provide a highly workable insulating sheet and a laminated structure using the insulating sheet.
  • a further limited object of the present invention is to provide an insulating sheet having high adhesion of a cured product to a bonding target member provided with a fine wiring pattern, and a laminated structure using the insulating sheet.
  • a further limited object of the present invention is to provide an insulating sheet having high heat resistance, voltage resistance and moisture resistance, and a laminated structure using the insulating sheet.
  • an insulating sheet used for bonding a thermal conductor having a thermal conductivity of 10 W / m ⁇ K or more to a conductive layer, wherein the polymer has a weight average molecular weight of 10,000 or more.
  • An insulating sheet is provided.
  • At least one of the polymer, the curable compound, and the curing agent contains a nitrogen atom.
  • curing agent contains a nitrogen atom.
  • the polymer preferably has an aromatic skeleton. Further, the curable compound preferably has an aromatic skeleton.
  • the polymer is preferably a phenoxy resin or an epoxy resin.
  • the curable compound has a hydroxyl group equivalent of 6000 or more.
  • the inorganic 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, magnesium carbonate and magnesium oxide. .
  • the inorganic filler preferably contains spherical alumina.
  • the inorganic filler preferably contains alumina having a purity by fluorescent X-ray analysis of 90.0% or more and 99.0% or less.
  • the inorganic filler preferably contains spherical alumina or crushed alumina having a purity by fluorescent X-ray analysis of 90.0% or more and 99.0% or less.
  • an elastomer that is a poly (meth) acrylic ester is further included.
  • the elastomer is preferably a polymer using butyl (meth) acrylate.
  • the curing agent preferably contains at least one of dicyandiamide and imidazole compounds.
  • curing agent contains a dicyandiamide.
  • the curing agent includes an imidazole compound.
  • 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 the surface opposite to the surface on which the body is laminated, and the insulating layer is formed by curing an insulating sheet configured according to the present invention.
  • the heat conductor is preferably a metal.
  • An insulating sheet according to the present invention includes a polymer having a weight average molecular weight of 10,000 or more, a curable compound having a molecular weight of 1200 or less and having an epoxy group or an oxetanyl group, a curing agent, and an inorganic filler.
  • Content of the said inorganic filler in 100 weight% is 60 weight% or more and 95 weight%
  • Content of the nitrogen atom contained in the component except the said inorganic filler in 100 weight% of insulating sheets Is 0.3% by weight or more and less than 3.0% by weight
  • the handling property and storage stability of the insulating sheet in the uncured state can be increased, and the heat dissipation of the cured product after curing is further increased.
  • the adhesion of the cured product 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.
  • the insulating sheet which concerns on this invention is an insulating sheet used in order to adhere
  • the insulating sheet according to the present invention includes a polymer (A) having a weight average molecular weight of 10,000 or more, a curable compound (B) having a molecular weight of 1200 or less and having an epoxy group or oxetanyl group, and a curing agent (C). And an inorganic filler (D).
  • the content of the inorganic filler (D) is 60% by weight or more and 95% by weight or less.
  • the content of nitrogen atoms contained in the component excluding the inorganic filler (D) in the insulating sheet is 0.3% by weight or more and less than 3.0% by weight.
  • the handling property and storage stability of the insulating sheet in an uncured state can be increased, the heat dissipation of the cured product obtained by curing the insulating sheet can be increased, and the cured product Adhesiveness can also be increased.
  • the adhesion target member contains copper
  • the adhesion of the cured product to the adhesion target member containing copper can be sufficiently increased.
  • the content of the inorganic filler (D) is large and the content of the nitrogen atom is within the above range even when the content is 60% by weight or more, handling properties, storage stability, adhesiveness and heat dissipation are improved. The balance can be improved sufficiently.
  • cured material of an insulating sheet has low adhesiveness with respect to the adhesion target member generally provided with the fine wiring pattern. Since the insulating sheet according to the present invention has the above composition, the adhesiveness of the cured product can be sufficiently increased even for a member to be bonded provided with fine wiring.
  • the heat resistance, voltage resistance and moisture resistance of the cured product of the insulating sheet can be improved.
  • the workability of the cured product of the insulating sheet can be improved.
  • the content of nitrogen atoms contained in the component excluding the inorganic filler (D) in the insulating sheet is more preferably 0.4% by weight or more, more preferably 2% by weight or less. Preferably it is 1 weight% or less.
  • the content of the nitrogen atom is 0.4% by weight or more, the adhesion to copper and the adhesion to the adhesion target member provided with the fine wiring pattern are further enhanced.
  • the nitrogen atom content is 2.5% by weight or less, the storage stability of the insulating sheet in an uncured state is further enhanced.
  • the nitrogen atom content does not include the nitrogen atom content contained in the inorganic filler (D).
  • the nitrogen atom content includes the nitrogen atom content contained in the polymer (A), the curable compound (B), and the curing agent (C). Furthermore, the content of nitrogen atoms includes the content of nitrogen atoms contained in the elastomer (E) described later.
  • the nitrogen atom content is the nitrogen atom content in the components in the insulating sheet (excluding the inorganic filler (D)).
  • the insulating sheet according to the present invention includes a polymer (A), a curable compound (B), and a curing agent ( It is preferable that at least one of C) contains a nitrogen atom.
  • the polymer (A) may or may not contain nitrogen.
  • the curable compound (B) may or may not contain nitrogen.
  • the curing agent (C) may or may not contain nitrogen.
  • the curing agent (C) contains a nitrogen atom. .
  • the insulating sheet according to the present invention is a poly (meth) acrylic ester in addition to the components (A) to (D). It is preferable to further contain an elastomer (E).
  • the elastomer (E) may or may not contain nitrogen atoms.
  • (Meth) acrylic acid indicates acrylic acid and methacrylic acid.
  • the polymer (A) contained in the insulating sheet according to the present invention is not particularly limited as long as the weight average molecular weight is 10,000 or more. From the viewpoint of further improving the heat resistance of the cured product, the polymer (A) preferably has an aromatic skeleton.
  • the polymer (A) may have an aromatic skeleton in any part of the whole polymer, and may have in the main chain skeleton. , May be present in the side chain.
  • the polymer (A) preferably has an aromatic skeleton in the main chain skeleton. In this case, the heat resistance of the cured product of the insulating sheet is further increased.
  • 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 hardened
  • thermoplastic resin and thermosetting resin are not particularly limited.
  • thermoplastic resins such as polyphenylene sulfide, polyarylate, polysulfone, polyethersulfone, polyetheretherketone, and polyetherketone.
  • 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.
  • 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 an epoxy resin, a styrene polymer, a (meth) acrylic polymer or a phenoxy resin, more preferably an epoxy resin or a phenoxy resin, and further preferably a phenoxy resin.
  • this preferable polymer the cured product of the insulating sheet is hardly oxidized and deteriorated, and the heat resistance is further enhanced.
  • the use of epoxy resin or phenoxy resin further increases the heat resistance of the cured product, and the use of phenoxy resin further increases the heat resistance of the cured product.
  • the epoxy resin is preferably an epoxy resin other than phenoxy resin.
  • the epoxy resin include styrene skeleton-containing epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin. , 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.
  • styrene polymer specifically, a homopolymer of a styrene monomer, a copolymer of a styrene monomer and an acrylic monomer, or the like can be used. Of these, styrene polymers having a styrene-glycidyl methacrylate structure are preferred.
  • styrene monomer examples include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, 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.
  • acrylic monomer examples include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, Examples include butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, ethyl ⁇ -hydroxyacrylate, propyl ⁇ -aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. It is done.
  • the phenoxy resin is specifically a resin obtained by reacting, for example, 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.
  • 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.
  • it has at least one skeleton of a fluorene skeleton and a biphenyl skeleton.
  • the phenoxy resin preferably has a polycyclic aromatic skeleton in the main chain.
  • the phenoxy resin preferably has at least one skeleton of the skeletons represented by the following formulas (11) to (16) in the main chain.
  • R 1 s may be the same or different and are 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 7 divalent hydrocarbon group, —O—, —S—, —SO 2 —, or —CO—.
  • 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
  • R 2 is a hydrogen atom, carbon number 1 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
  • m is an integer of 0 to 5.
  • 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 may be a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and l is an integer of 0 to 4.
  • R 5 and R 6 are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X 2 is —SO 2 —, —CH 2 —, —C (CH 3 ) 2. -Or -O-, and k is 0 or 1.
  • polymer (A) for example, a phenoxy resin represented by the following formula (17) or the following formula (18) is preferably used.
  • a 1 has a structure represented by any of the above formulas (11) to (13), and the structure thereof is 0 to 60 mol%, the structure represented by the above formula (12) is 5 to 95 mol%, and the structure represented by the above formula (13) is 5 to 95 mol%, and A 2 is a hydrogen atom or the above formula And n 1 is an average value of 25 to 500.
  • the structure represented by the formula (11) may not be included.
  • 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.
  • the resin is hardly thermally deteriorated.
  • the compatibility between the polymer (A) and another resin is increased. As a result, the handling property of the insulating sheet in an uncured state is further improved, and the heat resistance of the cured product of the insulating sheet is further increased.
  • 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.
  • the Tg of the phenoxy resin is not less than the above lower limit, the thermal deterioration of the resin can be further suppressed.
  • 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 insulating sheet in an uncured state and the heat resistance of the cured product of the insulating sheet 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.
  • the insulating sheet is hardly thermally deteriorated.
  • the compatibility between the polymer (A) and another resin is increased. As a result, the handling property of the insulating sheet in an uncured state is further improved, and the heat resistance of the cured product of the insulating sheet is further increased.
  • the polymer (A) may be added as a raw material, or may be a polymer produced by utilizing a reaction in each step such as stirring, coating, and drying during the production of the insulating sheet of the present invention. Good.
  • the hydroxyl group equivalent of the polymer (A) is preferably less than 6000. From the viewpoint of further improving the handleability of the insulating sheet in an uncured state, the hydroxyl equivalent of the polymer (A) is preferably 300 or more, more preferably 5500 or less, and even more preferably 5000 or less. It is preferable that the hydroxyl equivalent of the polymer (A) is not more than the above upper limit, and the hydroxyl equivalent of the curable compound (B) is not less than the lower limit described later.
  • 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 insulating sheet. It is preferable.
  • the content of the polymer (A) in 100% by weight of the total resin component X is more preferably 30% by weight or more, and more preferably 50% by weight or less.
  • the handling properties of the insulating sheet in an uncured state are further improved. Dispersion
  • the total resin component X refers to the total of the polymer (A), the curable compound (B), the curing agent (C), and other resin components added as necessary.
  • the total resin component X does not include the inorganic filler (D).
  • the total resin component X includes an elastomer (E) that is a poly (meth) acrylic acid ester.
  • the curable compound (B) contained in the insulating sheet according to the present invention is not particularly limited as long as it has a molecular weight of 1200 or less and has an epoxy group or an oxetanyl group.
  • the curable compound (B) having an epoxy group or oxetanyl group a conventionally known epoxy compound or oxetane compound can be used.
  • the curable compound (B) is preferably a monomer.
  • the curable compound (B) is cured by the action of the curing agent (C).
  • 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 oxetanyl 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.
  • the epoxy compound (B1) having an epoxy group examples 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.
  • the monomer examples 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.
  • 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.
  • Examples include naphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene.
  • 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,
  • 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) And methane and 1,2
  • 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.
  • oxetane compound (B2) having an oxetanyl 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.
  • an oxetane compound (B2) only 1 type may be used and 2 or more types may be used together.
  • the molecular weight of the curable compound (B) is 1200 or less.
  • the molecular weight of the curable compound (B) is preferably 200 or more, preferably 600 or less, more preferably 550.
  • the 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 insulating sheet is further enhanced.
  • the molecular weight of the curable compound (B) is not more than the above upper limit, the adhesiveness of the cured product is further enhanced.
  • the insulating sheet is hard and not easily brittle, and the adhesiveness of the cured product is further enhanced.
  • the molecular weight in the curable compound (B) means a molecular weight that can be calculated from the structural formula when it is not a polymer and when the structural formula can be specified. Means weight average molecular weight.
  • the hydroxyl group equivalent of the curable compound (B) is preferably 6000 or more.
  • the hydroxyl equivalent of the curable compound (B) is 6000 or more, even if curing proceeds during storage, the insulating sheet does not crack at the time of handling, and the insulating sheet in an uncured state Storage stability is also sufficiently high.
  • the hydroxyl equivalent of the curable compound (B) is more preferably 6500 or more, further preferably 7000 or more, and particularly preferably 15000. That's it.
  • the content of the curable compound (B) is preferably 10% by weight or more and 60% by weight or less.
  • the content of the curable compound (B) in 100% by weight of the total resin component X is more preferably 20% by weight or more, and more preferably 50% by weight or less.
  • the content of the curable compound (B) is not less than the above lower limit, the adhesiveness and heat resistance of the cured product are further increased.
  • the content of the curable compound (B) is not more than the above upper limit, the handling property of the insulating sheet is further enhanced.
  • the curing agent (C) contained in the insulating sheet according to the present invention is not particularly limited as long as the insulating sheet can be cured.
  • the curing agent (C) is preferably a thermosetting agent.
  • curing agent (C) only 1 type may be used and 2 or more types may be used together.
  • the curing agent (C) is a dicyandiamide and imidazole compound. It is preferable to contain at least one of the above, more preferably dicyandiamide, and more preferably both dicyandiamide and an imidazole compound. By using a dicyandiamide or an imidazole compound, it is easy to contain a lot of nitrogen atoms in the insulating sheet.
  • the curing agent (C) may be dicyandiamide or an imidazole compound. By using dicyandiamide, the adhesiveness of the cured product of the insulating sheet is further enhanced. From the viewpoint of further improving the heat resistance of the cured product and shortening the curing time, the curing agent (C) preferably contains an imidazole compound.
  • imidazole compound examples include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 ' -Mechi Imidazolyl- (1 ′)]-
  • the content of nitrogen atoms is preferably 10 in 100% by weight of all atoms in the curing agent. % By weight or more, more preferably 20% by weight or more, preferably 30% by weight or more, more preferably 80% by weight or less.
  • the content of nitrogen atoms contained in the curing agent (C) in 100% by weight of the insulating sheet is preferably 0.3% by weight or more, more preferably 0.4% by weight or more, more preferably 2% by weight or less.
  • the content of nitrogen atoms contained in the imidazole compound in the insulating sheet 100% by weight is preferably 1.3% by weight or more, more preferably 2% by weight. % Or more.
  • the content of the curing agent (C) is preferably 10% by weight or more and 40% by weight or less. In the total 100% by weight of all the resin components X, the content of the curing agent (C) is more preferably 12% by weight or more, and more preferably 25% by weight or less.
  • the content of the curing agent (C) is not less than the above lower limit, it is easy to sufficiently cure the insulating sheet.
  • 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 and adhesiveness of hardened
  • Dicyandiamide in a total of 100% by weight of the total resin component X in order to improve the handling property, storage stability, adhesiveness, heat resistance, voltage resistance and moisture resistance in a balanced manner and to further improve the adhesiveness.
  • the total content of imidazole and imidazole compound is preferably 10% by weight or more, more preferably 12% by weight or more, preferably 40% by weight or less, more preferably 25% by weight or less.
  • the insulating sheet preferably contains dicyandiamide and imidazole compound in a weight ratio of 1:99 to 99: 1, and 90:10 to 10:90. More preferred.
  • the blending ratio of dicyandiamide and imidazole compound is within the above range, handling property, storage stability, adhesiveness, heat resistance, voltage resistance, and moisture resistance can be effectively improved in a balanced manner, and further adhesiveness can be improved. Can be further increased.
  • the inorganic filler (D) contained in the insulating sheet according to the present invention is not particularly limited as long as the thermal conductivity is 10 W / m ⁇ K or more.
  • the thermal conductivity of the cured product can be increased.
  • the heat dissipation of the cured product is increased.
  • an inorganic filler (D) only 1 type may be used and 2 or more types may be used together.
  • the thermal conductivity of the inorganic 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 inorganic 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.
  • the inorganic filler (D) 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, magnesium carbonate and magnesium oxide. Is preferable, and at least one selected from the group consisting of alumina, crystalline silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide, magnesium carbonate and magnesium oxide is more preferable. By using these preferable fillers, the heat dissipation of the cured product can be further enhanced.
  • the magnesium carbonate is different from synthetic magnesite.
  • the inorganic filler (D) is 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.
  • the inorganic filler (D) may be a spherical filler or a crushed filler.
  • the inorganic 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 is further enhanced.
  • the inorganic filler (D) preferably contains spherical alumina.
  • the inorganic filler (D) preferably contains 50% by weight or more of spherical alumina, preferably 75% by weight or more, and contains 100% by weight or less. All of the inorganic filler (D) may be spherical alumina.
  • the inorganic filler (D) is made of alumina having a purity (alumina purity) by fluorescent X-ray analysis of 90.0% or more and 99.0% or less. It is preferable to include. In addition, when the purity exceeds 99.0%, the workability tends to be low. When the purity is 90.0% or more, the heat dissipation of the cured product is further enhanced.
  • the inorganic filler (D) preferably contains 50% by weight or more of alumina having a purity of 90.0 to 99.0%, preferably 75% by weight or more, and contains 100% by weight or less.
  • All of the inorganic fillers (D) may be alumina having a purity of 90.0 to 99.0%.
  • the purity (%) is the content (%) of alumina in 100% of the inorganic filler which is alumina to be blended.
  • alumina whose purity by fluorescent X-ray analysis is 90.0% or more and 99.0% or less is an inorganic substance whose purity by alumina X-ray analysis is 90.0% or more and 99.0% or less. It is a filler.
  • the inorganic filler (D) preferably contains spherical alumina or crushed alumina whose purity by fluorescent X-ray analysis is 90.0% or more and 99.0% or less. .
  • the inorganic filler (D) preferably contains 50% by weight or more of spherical alumina or crushed alumina having a purity of 90.0 to 99.0%, preferably 75% by weight or more, and contains 100% by weight or less. All of the inorganic fillers (D) may be spherical alumina or crushed alumina having a purity of 90.0 to 99.0%.
  • Crushed filler may be mentioned as the crushed filler.
  • 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.
  • the filler in the insulating sheet is likely to have a structure that is bridged or effectively brought close together. Therefore, the thermal conductivity of the cured product of the insulating sheet is further increased.
  • the crushed filler is generally cheaper than a normal filler. For this reason, the cost of an insulating sheet can be reduced by using the crushed filler.
  • the average particle size of the crushed filler is preferably 12 ⁇ m or less. When the average particle size is 12 ⁇ m or less, it is easy to disperse the crushed filler in the insulating sheet at a high density, and the dielectric breakdown characteristics of the cured product of the insulating sheet are further enhanced.
  • the average particle size of the crushed filler is more preferably 10 ⁇ m or less, and preferably 1 ⁇ m or more. When the average particle size of the crushed filler is not less than the above lower limit, it is easy 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 insulating 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 Lucas).
  • the average particle diameter of the spherical filler is preferably 0.1 ⁇ m or more and 40 ⁇ m or less.
  • the average particle size is 0.1 ⁇ m or more, the inorganic filler (D) can be easily filled at a high density.
  • the average particle size is 40 ⁇ m or less, the dielectric breakdown characteristics of the cured product are further enhanced.
  • the above-mentioned “average particle diameter” is an average particle diameter obtained from a volume average particle size distribution measurement result measured with a laser diffraction particle size distribution measuring apparatus.
  • the new Mohs hardness of the inorganic filler (D) is preferably 12 or less, more preferably 9 or less. When the new Mohs hardness of the inorganic filler (D) is 9 or less, the workability of the cured product is further enhanced.
  • the inorganic filler (D) was selected from the group consisting of synthetic magnesite, crystalline silica, zinc oxide, and magnesium oxide. It is preferable that there is at least one.
  • the content of the inorganic filler (D) in 100% by weight of the insulating sheet is 60% by weight or more. Moreover, content of the inorganic filler (D) in 100 weight% of insulating sheets is 95 weight% or less.
  • the content of the inorganic filler (D) in 100% by weight of the insulating sheet is preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 70% by weight or less.
  • the elastomer (E) contained in the insulating sheet according to the present invention is a poly (meth) acrylic ester.
  • the elastomer (E) that is the poly (meth) acrylate is not particularly limited.
  • Elastomers are compounds that exhibit rubber elasticity near room temperature. Only one type of elastomer (E) may be used, or two or more types may be used in combination.
  • an elastomer (E) which is a poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate Hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
  • polymerization components for obtaining an elastomer (E) that is a poly (meth) acrylic acid ester include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and maleic anhydride And epoxy group-containing monomers such as glycidyl acrylate and allyl glycidyl ether.
  • the elastomer (E) which is a poly (meth) acrylic acid ester is preferably a polymer using butyl (meth) acrylate, and butyl methacrylate is used. More preferred is a polymer.
  • the “polymer” includes a copolymer.
  • the elastomer (E) may be included in the form of rubber particles. By adding the elastomer (E) in the form of rubber particles, the stress relaxation property and flexibility of the insulating sheet can be enhanced without impairing the heat resistance.
  • the content of the elastomer (E) is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 30% by weight or less.
  • the content of the elastomer (E) is equal to or more than the above lower limit, the flexibility of the cured product is further increased, and the cooling cycle reliability is further increased.
  • the content of the elastomer (E) is not more than the above upper limit, the heat resistance of the cured product is further increased.
  • the insulating 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.
  • 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.
  • 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.
  • 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 insulating sheet is further enhanced.
  • 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.
  • the dispersant examples 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.
  • the said dispersing agent only 1 type may be used and 2 or more types may be used together.
  • 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 10% by weight. % By weight or less.
  • the content of the dispersant is not less than the above lower limit and not more than the upper limit, aggregation of the inorganic filler (D) is difficult to occur, and the heat dissipation and dielectric breakdown characteristics of the cured product are further enhanced.
  • the insulating sheet according to the present invention may contain a base material such as glass cloth, glass nonwoven fabric, and aramid nonwoven fabric.
  • the insulating sheet has a self-supporting property at room temperature (23 ° C.) and an excellent handling property. Therefore, the insulating sheet preferably does not contain a base material, and particularly preferably does not contain glass cloth.
  • the thickness of an insulating sheet can be made thin and the thermal conductivity of hardened
  • an insulating sheet does not contain the said base material, various processes, such as a laser processing or a drilling process, can also be easily performed to an insulating sheet as needed.
  • 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.
  • the insulating sheet according to the present invention may contain a tackifier, a plasticizer, a coupling agent, a thixotropic agent, a flame retardant, a photosensitizer, a colorant, and the like as necessary.
  • the insulating 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 manufacturing method of the insulating sheet which concerns on this invention is not specifically limited.
  • the insulating sheet can be obtained, for example, by forming a mixture obtained by mixing 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 insulating sheet is not particularly limited.
  • the thickness of the insulating sheet is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, further preferably 70 ⁇ m or more, preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and still more preferably 120 ⁇ m or less.
  • the thickness is not less than the above lower limit, the insulating property of the cured product of the insulating sheet is increased.
  • the thickness is less than or equal to the above upper limit, the heat dissipation becomes high when the metal body is bonded to the conductive layer.
  • the glass transition temperature Tg of the insulating sheet in the uncured state is preferably 25 ° C. or lower.
  • the glass transition temperature is 25 ° C. or lower, the insulating sheet is hard and not easily brittle at room temperature. For this reason, the handleability of the insulating sheet in an uncured state is enhanced.
  • the thermal conductivity of the cured product of the insulating 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.
  • cured material of an insulating sheet becomes high enough that heat conductivity is more than the said minimum.
  • the dielectric breakdown voltage of the cured product of the insulating sheet is preferably 25 kV / mm or more, more preferably 30 kV / mm or more, still more preferably 40 kV / mm or more, still more preferably 50 kV / mm or more, and particularly preferably 80 kV / mm or more. It is. If the dielectric breakdown voltage is too low, the insulating property may be lowered when the insulating sheet is used for a large current application such as for a power element.
  • the insulating sheet according to the present invention constitutes an insulating layer of a laminated structure in which a conductive layer is laminated on at least one surface of a heat conductor having a thermal conductivity of 10 W / m ⁇ K or more via an insulating layer. Is preferably used.
  • the laminated structure 1 shown in FIG. 1 includes a heat conductor 2, an insulating layer 3 laminated on the first surface 2a of the heat conductor 2, and a surface on which the heat conductor 2 of the insulating layer 3 is laminated. And a conductive layer 4 laminated on the opposite surface.
  • the insulating layer and the conductive layer are not laminated on the second surface 2b opposite to the first surface 2a of the heat conductor 2.
  • the insulating layer 3 is formed by curing the insulating sheet according to the present invention.
  • the heat conductivity of the heat conductor 2 is 10 W / m ⁇ K or more.
  • the insulating layer and the conductive layer are laminated in this order on at least one surface of the heat conductor, and the insulating layer and the conductive layer are laminated in this order on the other surface of the heat conductor. Good.
  • 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.
  • the laminated structure 1 can be obtained.
  • the thermal conductor having a thermal conductivity of 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.
  • 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 insulating sheet according to the present invention is suitably used for bonding a heat 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.
  • the insulating sheet according to the present invention adheres a heat conductor having a thermal conductivity of 10 W / m ⁇ K or more to a conductive layer of an electronic component device in which electronic component elements other than semiconductor elements are mounted on a substrate. Also preferably used.
  • the insulating sheet of this invention is used suitably for such a use.
  • measuring agent (C) (1) Dicyandiamide (Nippon Carbite, trade name: DD, nitrogen atom content 66.6% by weight) (2) Isocyanur-modified solid dispersion type imidazole (imidazole curing accelerator, manufactured by Shikoku Kasei Co., Ltd., trade name: 2MZA-PW, nitrogen atom content 44.7% by weight) (3) Biphenyl skeleton phenol resin (Madewa Kasei Co., Ltd., trade name: MEH-7851-S)
  • Elastomer (E) which is a poly (meth) acrylic ester (1) MMA / BMA elastomer (manufactured by Mitsubishi Rayon Co., Ltd., trade name: KW4426, rubber fine particles having a shell formed of methyl methacrylate and a core formed of n-butyl methacrylate, average particle size of 5 ⁇ m) (2) BMA elastomer (a polymer using n-butyl methacrylate, manufactured by Negami Kogyo Co., Ltd., trade name: Hyperl M-6003) (3) Acrylic polymer (butyl acrylate / ethyl acrylate / acrylonitrile terpolymer, manufactured by Nagase Chemtech Co., Ltd., trade name: WS-023)
  • Epoxysilane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE403
  • Examples 1 to 22 and Comparative Examples 1 to 5 Using a homodisper type stirrer, each raw material was blended in the proportions shown in Tables 1 and 2 below (blending unit is parts by weight) and kneaded to prepare an insulating material.
  • the insulating material was applied to a release PET sheet having a thickness of 50 ⁇ m so as to have a thickness of 100 ⁇ m, and dried in an oven at 90 ° C. for 30 minutes to produce an insulating sheet on the PET sheet.
  • Nitrogen atom content An uncured insulation sheet was thermally decomposed at a sample furnace temperature of 950 ° C. using a micro coder JM-10 manufactured by J Science Lab. The content (% by weight) of nitrogen atoms contained in the components excluding the inorganic filler in the sheet was measured.
  • ⁇ The insulating sheet is not deformed and can be easily peeled.
  • ⁇ The insulating sheet can be peeled, but the sheet is stretched or broken.
  • ⁇ The insulating sheet cannot be peeled.
  • Insulation sheet is not deformed and can be easily peeled
  • Insulation sheet can be peeled off, but chipping or cracking occurs during peeling
  • ⁇ Chipping or cracking occurs during peeling and the insulating sheet cannot be peeled off
  • Peel strength A (adhesiveness) An insulating sheet is sandwiched between an aluminum plate having a thickness of 1 mm and a middle profile electrolytic copper foil having a thickness of 35 ⁇ m, and the insulating sheet is held at 120 ° C. for 1 hour and further at 200 ° C. for 1 hour while maintaining a pressure of 4 MPa with a vacuum press. Press-cured to form a copper-clad laminate. The copper foil of the obtained copper-clad laminate was etched to form a copper foil strip having a width of 10 mm. The copper foil was peeled from the substrate at an angle of 90 ° C. at a pulling rate of 50 mm / min, and the peel strength A was measured.
  • solder heat resistance test (heat resistance) The copper-clad laminate obtained by the evaluation of (6) peeling strength A was cut out to 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.
  • Dielectric breakdown voltage (withstand voltage)
  • the insulating sheet was cut into a size of 100 mm ⁇ 100 mm to obtain a test sample.
  • the obtained test sample was cured in an oven at 120 ° C. for 1 hour and further in an oven at 200 ° C. for 1 hour to obtain a cured product of an insulating sheet.
  • An AC voltage was applied using a withstand voltage tester (MODEL7473, manufactured by EXTECH Electronics) so that the voltage increased at a rate of 1 kV / second between the cured products of the insulating sheet.
  • the voltage at which the cured product of the insulating sheet was broken was defined as the dielectric breakdown voltage.
  • Cooling cycle test The copper-clad laminate obtained by the evaluation of the above (6) peel strength A was cut into a size of 100 mm ⁇ 100 mm and the copper foil was peeled off to obtain a test sample. Using the test sample, a 500-cycle or 1000-cycle thermal cycle test is performed using a one-chamber type thermal cycle tester (WINTECH NT510, manufactured by ETACH) at -40 ° C, 20 minutes, and 125 ° C for 20 minutes. It was. The presence or absence of cracks on the surface of the insulating layer formed by the insulating sheet after the test was observed with an optical microscope (TRANSFORMER-XN, manufactured by Nikon).
  • WINTECH NT510 manufactured by ETACH
  • Tables 1 and 2 below show the composition and evaluation results of the insulating material for forming the insulating sheet.
  • * 1 indicates the content (% by weight) of the total resin component X in a total of 100% by weight.
  • * 2 indicates the content (% by weight) of nitrogen atoms contained in the component excluding the inorganic filler in the insulating sheet in 100% by weight of the insulating sheet. “-” Indicates that evaluation is not performed.
  • the following peel strength B adheresiveness
  • the adhesiveness is hardly exhibited.

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  • Insulating Bodies (AREA)

Abstract

L'invention porte sur une feuille isolante qui peut accroître l'aptitude à la manipulation et la stabilité au stockage dans un état non durci et, en outre, peut accroître les caractéristiques de dissipation de chaleur et la capacité d'adhérence de l'article durci après durcissement. Cette feuille isolante est utilisée pour amener un conducteur thermique ayant une conductivité thermique de 10 W/m·K ou plus à adhérer à une couche électroconductrice. Cette feuille isolante contient un polymère ayant un poids moléculaire moyen en poids de 10 000 ou plus, un composé durcissable qui a un poids moléculaire de 1 200 ou moins et un groupe époxy ou un groupe oxétanyle, un agent de durcissement et une charge inorganique. Dans 100 % en poids de la feuille isolante, la teneur en charge inorganique est de 60 % en poids ou plus et de 95 % en volume ou moins. Dans 100 % en poids de la feuille isolante, la teneur en atomes d'azote inclus dans les composants de la feuille isolante, à l'exception de la charge inorganique, est de 0,3 % en poids à moins de 3,0 % en poids.
PCT/JP2010/071540 2010-12-02 2010-12-02 Feuille isolante et structure stratifiée Ceased WO2012073360A1 (fr)

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JP2014232854A (ja) * 2013-05-30 2014-12-11 住友ベークライト株式会社 半導体装置
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JP2014156531A (ja) * 2013-02-15 2014-08-28 Hitachi Chemical Co Ltd エポキシ樹脂組成物、接着シート及び半導体素子
JP2014232854A (ja) * 2013-05-30 2014-12-11 住友ベークライト株式会社 半導体装置
JP2019116625A (ja) * 2014-03-31 2019-07-18 ナミックス株式会社 樹脂組成物、接着フィルム、および半導体装置
WO2016146796A1 (fr) * 2015-03-17 2016-09-22 Abb Technology Ltd Matériau inorganique d'isolation électrique
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