WO2016125664A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2016125664A1
WO2016125664A1 PCT/JP2016/052394 JP2016052394W WO2016125664A1 WO 2016125664 A1 WO2016125664 A1 WO 2016125664A1 JP 2016052394 W JP2016052394 W JP 2016052394W WO 2016125664 A1 WO2016125664 A1 WO 2016125664A1
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WIPO (PCT)
Prior art keywords
resin composition
component
insulating layer
mass
layer
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PCT/JP2016/052394
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English (en)
Japanese (ja)
Inventor
達也 本間
英恵 奥山
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味の素株式会社
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Priority to JP2016573308A priority Critical patent/JP6772841B2/ja
Publication of WO2016125664A1 publication Critical patent/WO2016125664A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/40—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item

Definitions

  • the present invention relates to a resin composition. Furthermore, it is related with an adhesive film, a printed wiring board, a power semiconductor device, and a laminated body.
  • Patent Document 1 discloses a technique for forming an insulating layer of a printed wiring board by curing a high thermal conductive resin composition containing a resin and an inorganic filler having a specific average particle diameter.
  • Patent Document 2 in order to improve the heat dissipation of a semiconductor module using a power semiconductor element that generates a particularly large amount of heat (also referred to as “power semiconductor element”), the semiconductor module is bonded to a metal heat sink with an adhesive. A power semiconductor device obtained by bonding is disclosed.
  • the present inventors examined the thermal diffusivity of the insulating layer in order to more efficiently diffuse the heat generated by the semiconductor element.
  • an insulating layer is formed by curing a resin composition containing an inorganic filler
  • the thermal diffusibility of the resulting insulating layer is in a trade-off relationship with the adhesion strength to the metal layer (conductor layer).
  • the inventors have found. Specifically, by increasing the content of the inorganic filler in the resin composition, the thermal diffusibility of the resulting insulating layer can be improved, but the inorganic filler is sufficiently developed to exhibit sufficient thermal diffusivity. It was found that when the content is increased, the obtained insulating layer is inferior in adhesion strength to the metal layer (conductor layer).
  • An object of the present invention is to provide a resin composition that provides a cured product that exhibits sufficient thermal diffusivity and exhibits good adhesion strength to a metal layer.
  • a resin composition comprising (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler, (B) a component contains a liquid phenol type hardening
  • a resin composition containing a filler is (C1) an inorganic filler having an average particle size of 0.1 ⁇ m or more and less than 3 ⁇ m, (C2) an inorganic filler having an average particle size of 3 ⁇ m or more and less than 10 ⁇ m, and (C3) an inorganic material having an average particle size of 10 ⁇ m or more and 35 ⁇ m or less.
  • the thickness of the resin composition layer is (d c3 +45) ⁇ m to 200 ⁇ m, when the average particle diameter of the component (C3) is d c3 ( ⁇ m).
  • Adhesive film [15] The adhesive film according to any one of [12] to [14], which is for high heat conduction. [16] The adhesive film according to any one of [12] to [15], which is used for bonding a metal radiator and a semiconductor module. [17] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [11].
  • the thermal conductivity of the insulating layer is 8 W / m ⁇ K or more
  • apparatus. [21] A laminate of an insulating layer and a metal layer, A laminate in which the thermal conductivity of the insulating layer is 8 W / m ⁇ K or more and the adhesion strength between the insulating layer and the metal layer is 0.5 kgf / cm or more.
  • the heat generated by the semiconductor element can be efficiently diffused.
  • the resin composition of the present invention provides a cured product excellent in both thermal diffusibility and adhesion strength to the metal layer, it is extremely useful as an adhesive for bonding a semiconductor module and a metal radiator in a power semiconductor device. .
  • the resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, (B) a component includes a liquid phenolic curing agent, and (C) a component is (C1 And (C2) an inorganic filler having an average particle size of 3 ⁇ m or more and less than 10 ⁇ m, and (C3) an inorganic filler having an average particle size of 10 ⁇ m or more and 35 ⁇ m or less. To do.
  • the thermal diffusibility of the resulting insulating layer has a trade-off relationship with the adhesion strength to the metal layer (conductor layer).
  • the resin composition of the present invention containing the specific components (A) to (C) in combination realizes a cured product (insulating layer) excellent in both thermal diffusibility and adhesion strength to the metal layer. Can do.
  • epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin
  • the epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule.
  • the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule.
  • the epoxy resin is at a temperature of 20 ° C. It preferably contains a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”).
  • the liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule.
  • the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.
  • the epoxy resin may include a solid epoxy resin (also referred to as “solid epoxy resin”) at a temperature of 20 ° C.
  • the solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule.
  • the determination of whether the target component is liquid or solid at a temperature of 20 ° C. is performed when the target component is in a single state (that is, a state that does not substantially include other components such as a solvent).
  • Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, bifunctional aliphatic epoxy resin, cyclohexane di A methanol type epoxy resin and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bifunctional aliphatic epoxy resin, and a naphthalene type epoxy resin are more preferable.
  • liquid epoxy resin examples include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828EL”, “828US” manufactured by Mitsubishi Chemical Corporation. "(Bisphenol A type epoxy resin)”, “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7410” (bifunctional aliphatic epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, And bisphenol AF type epoxy resin is more preferable.
  • solid epoxy resin examples include “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690”, “N-695” (cresol novolak) manufactured by DIC Corporation.
  • Type epoxy resin “HP7200”, “HP7200H”, “HP7200HH” (dicyclopentadiene type epoxy resin), “EXA7311”, “EXA7311-G3”, “EXA7311-G4”, “EXA7311-G4S”, “HP6000” (Naphthylene ether type epoxy resin), “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000”, “ NC3000L ”,“ NC3100 ”(Bifeni Type epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumi
  • the content of the epoxy resin in the resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more or 5% by mass or more.
  • the upper limit of the content of the epoxy resin is not particularly limited, but is preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass. Or 30% by mass or less.
  • content of each component which comprises a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.
  • the epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened
  • the epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
  • the weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500.
  • the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
  • the curing agent includes a liquid phenolic curing agent.
  • curing agent means a liquid phenol type hardening
  • the phenolic hydroxyl group equivalent of the liquid phenolic curing agent is preferably 50 to 1000, more preferably 70 to 800, and still more preferably 90 to 600 from the viewpoint of obtaining an insulating layer exhibiting good adhesion strength to the metal layer.
  • the phenolic hydroxyl group equivalent is the mass of a resin containing 1 equivalent of a phenolic hydroxyl group.
  • the weight average molecular weight of the liquid phenolic curing agent is preferably 100 to 4500, more preferably 200 to 4000, and still more preferably 300 to 3000.
  • curing agent is a weight average molecular weight of polystyrene conversion measured by GPC method.
  • liquid phenolic curing agent examples include liquid phenol represented by the formula (1).
  • R 1 independently represents a hydrogen atom, an alkyl group, or an alkenyl group
  • R 2 and R 3 each independently represent a hydrogen atom or an alkyl group
  • j represents an integer of 0 to 5
  • the plurality of R 1 to R 3 may be the same or different.
  • the number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3.
  • the alkenyl group is preferably a 2-propenyl group (allyl group).
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4, 1 to 3, or 1.
  • R 1 is an alkyl group or an alkenyl group.
  • the number of alkyl groups or alkenyl groups in formula (1) is preferably 1 or more. More preferably, it contains one or two alkyl groups and / or alkenyl groups for one benzene ring in formula (1), and more preferably for one benzene ring in formula (1).
  • R 1 preferably represents a hydrogen atom or an alkenyl group, and more preferably represents a hydrogen atom or an allyl group.
  • R 2 and R 3 preferably represent a hydrogen atom.
  • a plurality of R 1 may be the same or different from each other. The same applies to R 2 to R 3 .
  • liquid phenolic curing agent examples include “ACG-1”, “APG-1”, “ELP-30”, “ELC” manufactured by Gunei Chemical Industry Co., Ltd., and “MEH” manufactured by Meiwa Kasei Co., Ltd. -8000 "can be used.
  • the (B) curing agent may contain another curing agent in addition to the liquid phenolic curing agent.
  • Such other curing agents are not particularly limited as long as they have a function of curing the epoxy resin, and include, for example, solid phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and Examples include cyanate ester-based curing agents.
  • Another hardening agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the solid phenol-based curing agent refers to a solid phenol-based curing agent at a temperature of 20 ° C.
  • a phenol-based curing agent or a naphthol-based curing agent containing both a triazine structure and a novolak structure is preferable. These may be used alone or in combination of two or more.
  • Examples of commercially available solid phenol-based curing agents and naphthol-based curing agents include “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • the active ester curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy compound ester in one molecule.
  • a compound having two or more in the above is preferably used.
  • the active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned.
  • cyanate ester type hardening agent for example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, And bisphenol F type, bisphenol S type, and the like) and cyanate ester-based curing agents, and prepolymers in which these are partially triazines.
  • novolak type phenol novolak type, alkylphenol novolak type, etc.
  • cyanate ester type hardening agent dicyclopentadiene type cyanate ester type hardening agent
  • bisphenol type bisphenol A type, And bisphenol F type, bisphenol S type, and the like
  • cyanate ester-based curing agents and prepolymers in which these are partially triazines.
  • Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl.
  • cyanate ester curing agents examples include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins) and “BA230” (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Or a prepolymer which is all triazine-modified into a trimer).
  • the amount ratio of (A) epoxy resin to (B) curing agent is [total number of epoxy groups of epoxy resin]: [reactive group of curing agent] from the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer.
  • the ratio of the total number] is preferably in the range of 1: 0.2 to 1: 2, more preferably in the range of 1: 0.3 to 1: 1.5, and in the range of 1: 0.4 to 1: 1. Is more preferable.
  • the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent.
  • the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins
  • the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents.
  • the average particle diameter of the component (C1) is dc1 ( ⁇ m)
  • the average particle diameter of the component (C2) is dc2 ( ⁇ m).
  • D c1 and d c2 preferably satisfy the relationship d c2 ⁇ d c1 ⁇ 0.5, more preferably satisfy the relationship d c2 ⁇ d c1 ⁇ 1.0, and d c2 ⁇ d More preferably, the relationship of c1 ⁇ 1.5, d c2 ⁇ d c1 ⁇ 2.0, d c2 ⁇ d c1 ⁇ 2.5, or d c2 ⁇ d c1 ⁇ 3.0 is satisfied.
  • the upper limit of the difference d c2 -d c1 is preferably 9.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, 6.0 or less, or 5.0 or less.
  • d c2 and d c3 are d c3 -d
  • d c2 ⁇ 5.0 more preferably satisfy the relationship of d c3 ⁇ d c2 ⁇ 7.0, d c3 ⁇ d c2 ⁇ 9.0, d c3 ⁇ d c2 ⁇ 10.0
  • the relationship d c3 -d c2 ⁇ 12.0, d c3 -d c2 ⁇ 14.0, or d c3 -d c2 ⁇ 15.0 is satisfied.
  • the upper limit of the difference d c3 -d c2 is preferably 30.0 or less, more preferably 28.0 or less, still more preferably 26.0 or less, 24.0 or less, 22.0 or less, or 20.0 or
  • the average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter.
  • an inorganic filler dispersed in water by ultrasonic waves can be preferably used.
  • As a laser diffraction scattering type particle size distribution measuring device “LA-500”, “LA-950” manufactured by Horiba, Ltd., etc. can be used.
  • the (C1) component contributes to the improvement of the thermal diffusibility of the resin composition (and thus the insulating layer) by filling the gap between the (C2) component and the (C3) component.
  • the component (C1) also exhibits an effect of suppressing an increase in melt viscosity when the total content of the component (C) is high in combination with the component (C2) and the component (C3).
  • the content of the component (C1) is a viewpoint that can suppress an excessive increase in melt viscosity even when the content of the component (C) is high, thermal diffusion From the viewpoint of obtaining an insulating layer having excellent properties, preferably 5% by mass or more, more preferably 6% by mass or more, still more preferably 8% by mass or more, 10% by mass or more, 12% by mass or more, 14% by mass or more, or 15 It is at least mass%.
  • the upper limit of the content of the component (C1) reduces the diffusion resistance at the interface (between the inorganic filler and the inorganic filler and between the inorganic filler and the metal layer) when the heat generated by the semiconductor element diffuses through the printed wiring board. From the viewpoint, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
  • the (C2) component contributes to the improvement of the thermal diffusibility of the resin composition (and thus the insulating layer) by filling the gap between the (C3) component.
  • the component (C2) also has an average particle size larger than that of the component (C1) and contributes to a decrease in diffusion resistance at the interface during thermal diffusion.
  • the content of the component (C) is 100% by mass
  • the content of the component (C2) is preferably 5% by mass or more, more preferably 6% by mass or more from the viewpoint of obtaining an insulating layer having excellent thermal diffusibility. More preferably, they are 8 mass% or more, 10 mass% or more, 12 mass% or more, 14 mass% or more, or 15 mass% or more.
  • the upper limit of the content of the component (C2) is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less, from the viewpoint of suppressing an excessive increase in melt viscosity.
  • the component (C3) has a larger average particle size than the components (C1) and (C2), reduces the diffusion resistance at the interface during thermal diffusion, and improves the thermal diffusivity of the resin composition (and thus the insulating layer). A big contribution.
  • the content of the component (C) is 100% by mass
  • the content of the component (C3) is preferably 20% by mass or more, more preferably 30% by mass or more from the viewpoint of obtaining an insulating layer having excellent thermal diffusibility. More preferably, they are 40 mass% or more, 45 mass% or more, 50 mass% or more, 55 mass% or more, or 60 mass% or more.
  • the upper limit of the content of the component (C3) is preferably 90% by mass or less, more preferably 85%, from the viewpoint of obtaining a resin composition that maintains a good filling state of the component (C) and is excellent in lamination properties and thermal diffusibility. It is 80 mass% or less, More preferably, it is 75 mass% or less, or 70 mass% or less.
  • contents of the components (C1), (C2), and (C3) in the component (C) are as described above. From the viewpoint of obtaining an insulating layer that is further excellent in both thermal diffusibility and adhesion strength to the metal layer, It is preferable that content of (C3) component is the highest.
  • inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitride.
  • zirconium acid and zirconium tungstate phosphate examples include zirconium acid and zirconium tungstate phosphate.
  • the inorganic filler preferably has a thermal conductivity of 25 W / m ⁇ K or more, more preferably 50 W / m ⁇ K or more, and even more preferably 75 W / m ⁇ K or more. Even more preferably 100 W / m ⁇ K or more, particularly preferably 125 W / m ⁇ K or more, 150 W / m ⁇ K or more, 175 W / m ⁇ K or more, 200 W / m ⁇ K or more, or 225 W / m ⁇ K or more. It is preferable to include an inorganic filler.
  • the upper limit of the thermal conductivity is not particularly limited, but is usually 400 W / m ⁇ K or less.
  • the thermal conductivity of the inorganic filler can be measured by known methods such as a heat flow meter method and a temperature wave analysis method.
  • the inorganic filler preferably includes an inorganic filler with high thermal conductivity selected from the group consisting of aluminum nitride, alumina, boron nitride, silicon nitride, and silicon carbide, among which aluminum nitride, Alternatively, it is preferable to contain alumina.
  • aluminum nitride examples include “Shape H” manufactured by Tokuyama Corporation
  • silicon nitride examples include “SN-9S” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Examples of commercially available alumina products include “AHP300” manufactured by Nippon Light Metal Co., Ltd. and “Arnabeads (registered trademark) CB” manufactured by Showa Denko Co., Ltd. (for example, “CB-P05”, “CB-A30S”). It is done.
  • (C1) component, (C2) component and (C3) component may be formed from the same material, and may be formed from mutually different materials.
  • each of the (C1) component, the (C2) component, and the (C3) component may be formed of one type of material or may be formed of a combination of two or more types of materials.
  • (C3) component contains an inorganic filler with high thermal conductivity
  • (C3) component and (C2) component contain an inorganic filler with high thermal conductivity
  • (C3 It is more preferable that all of the component (C), the component (C2) and the component (C1) contain an inorganic filler having a high thermal conductivity.
  • Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. And may be treated with one or more surface treatment agents.
  • surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
  • the degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
  • Carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, 0.1 mg / m 2 or more preferably, 0.2 mg / m 2 The above is more preferable.
  • 1 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the sheet form. preferable.
  • the amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.
  • EMIA-320V manufactured by Horiba, Ltd.
  • the content of the inorganic filler in the resin composition is preferably 60% by volume or more, more preferably, when the nonvolatile component in the resin composition is 100% by volume. 65% by volume or more.
  • the content of the inorganic filler can be further increased without lowering the adhesion strength to the metal layer.
  • the content of the inorganic filler in the resin composition may be increased to 66 volume% or more, 68 volume% or more, 70 volume% or more, 72 volume% or more, 74 volume% or more, or 75 volume% or more.
  • the upper limit of the content of the inorganic filler in the resin composition is preferably 90% by volume or less, more preferably 85% by volume or less, from the viewpoint of the mechanical strength of the obtained insulating layer.
  • the resin composition of the present invention may further contain a curing accelerator.
  • a curing accelerator By using a curing accelerator, the adhesion strength to the metal layer can be increased.
  • the curing accelerator examples include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like.
  • a curing accelerator and an imidazole curing accelerator are preferred, and a phosphorus curing accelerator is more preferred.
  • a hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Examples of the phosphorus curing accelerator include tetra-substituted phosphonium salts and phosphines (eg, triphenylphosphine, tripalatolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, 1,4-bisdiphenylphosphinobutane). Triphenylphosphine and tetra-substituted phosphonium salts are preferred, and tetra-substituted phosphonium salts are more preferred.
  • phosphines eg, triphenylphosphine, tripalatolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, 1,4-bisdiphenylphosphinobutane.
  • Triphenylphosphine and tetra-substituted phosphonium salts are preferred,
  • the tetra-substituted phosphonium salt is preferably one or more cations selected from tetraalkylphosphonium cations (for example, tetrabutylphosphonium, tributylhexylphosphonium, butyltriphenylphosphonium, etc.) and tetraarylphosphonium cations (for example, tetraphenylphosphonium, etc.). It is formed.
  • tetraalkylphosphonium cations for example, tetrabutylphosphonium, tributylhexylphosphonium, butyltriphenylphosphonium, etc.
  • tetraarylphosphonium cations for example, tetraphenylphosphonium, etc.
  • the tetra-substituted phosphonium salt is preferably a tetra-substituted borate anion (eg, tetraphenylborate anion), thiocyanate anion, dicyanamide anion, 4,4′-dihydroxydiphenylsulfone anion, amino acid ion (eg, aspartate ion, glutamate ion, Glycine ion, alanine ion, phenylalanine ion), N-acylamino acid ion (eg, N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion), carboxylate anion (eg, formate ion, acetate ion, decane) Acid ion, 2-pyrrolidone-5-carboxylate ion, ⁇ -lipoic acid ion, lactate ion, tartrate ion
  • amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,0) -undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
  • imidazole curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- -Phenylimidazolium trimellitate, 2,4
  • imidazole curing accelerator Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.
  • guanidine curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- o- tolyl) biguanide
  • the metal-based curing accelerator examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complex examples include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
  • the content of the curing accelerator in the resin composition is in the range of 0.05% by mass to 3% by mass when the total of the non-volatile components of (A) the epoxy resin and (B) the curing agent is 100% by mass. It is preferable to do.
  • the resin composition of the present invention may further contain a carbodiimide compound.
  • the present inventors have found that by using a carbodiimide compound in combination with the above components (A) to (C), a resin composition (and consequently an insulating layer) exhibiting better adhesion strength to the metal layer can be realized. It was.
  • a carbodiimide compound is a compound having one or more carbodiimide groups (—N ⁇ C ⁇ N—) in one molecule. From the viewpoint of increasing the adhesion strength to the metal layer, the carbodiimide compound is preferably a compound having two or more carbodiimide groups in one molecule.
  • a carbodiimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).
  • X represents an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent.
  • P represents an integer of 1 to 5.
  • X is an alkylene group or a cycloalkylene group from the viewpoint of realizing a resin composition (and consequently an insulating layer) that exhibits better adhesion strength to the metal layer in combination with the components (A) to (C).
  • a resin composition and consequently an insulating layer
  • X may have a substituent.
  • a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group are mentioned.
  • the number of carbon atoms of the alkyl group or alkoxy group used as a substituent is preferably 1-20, more preferably 1-10, still more preferably 1-6, 1-4, or 1-3.
  • the number of carbon atoms of the cycloalkyl group or cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6.
  • the number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10.
  • the number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and still more preferably 6 to 10.
  • Acyl group used as a substituent of the formula: -C ( O) group (wherein, R 1 represents an alkyl group or an aryl group.) Represented by -R 1 refers.
  • the number of carbon atoms of the alkyl group represented by R 1 is preferably 1-20, more preferably 1-10, still more preferably 1-6, 1-4, or 1-3.
  • the number of carbon atoms of the aryl group represented by R 1 is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and still more preferably 6 to 10.
  • the acyloxy group used as a substituent refers to a group represented by the formula: —O—C ( ⁇ O) —R 1 (wherein R 1 has the same meaning as described above). Especially, as a substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.
  • p is preferably 1 to 4, more preferably 2 to 4, and still more preferably 2 or 3.
  • X when there are a plurality of X, they may be the same or different.
  • at least one X is an alkylene group or a cycloalkylene group, and these may have a substituent.
  • the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, when the mass of the entire carbodiimide compound is 100% by mass. More preferably, the structural unit represented by the formula (2) is contained at 80% by mass or more or 90% by mass or more.
  • the carbodiimide compound may consist essentially of the structural unit represented by the formula (2) except for the terminal structure. Although it does not specifically limit as a terminal structure of a carbodiimide compound, For example, an alkyl group, a cycloalkyl group, and an aryl group are mentioned, These may have a substituent.
  • the alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituent that the group represented by X may have.
  • the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.
  • carbodiimide compound a commercially available product may be used.
  • Commercially available carbodiimide compounds include, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., Starbuxol (registered trademark) manufactured by Rhein Chemie P, P400, and Hikazil 510.
  • the content of the carbodiimide compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass. That's it.
  • the upper limit of the content of the carbodiimide compound is not particularly limited, it can usually be 5% by mass or less, 3% by mass or less, 1% by mass or less.
  • the resin composition of the present invention may further contain a thermoplastic resin.
  • a thermoplastic resin By using a thermoplastic resin, an adhesive film having sufficient flexibility and excellent handleability can be obtained, and a resin composition layer (and thus an insulating layer) exhibiting good adhesion strength to a metal layer can be obtained. Obtainable.
  • thermoplastic resin examples include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether.
  • a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000.
  • the weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • the polystyrene-converted weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the mobile phase.
  • phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene
  • the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
  • a phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation).
  • “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, “YL7290”, “YL7482” and the like can be mentioned.
  • polyvinyl acetal resin examples include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable.
  • Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd.'s S-REC BH series, BX series, KS series, BL series, BM series and the like.
  • polyimide resins include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.
  • Specific examples of the polyimide resin also include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton.
  • modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).
  • polyamide-imide resin examples include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd.
  • polyamideimide resin also include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.
  • polyethersulfone resin examples include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
  • polysulfone resin examples include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.
  • the thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.
  • the content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass.
  • the flame retardant examples include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide.
  • a flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 0.8% by mass to 9% by mass.
  • any organic filler that can be used for forming an insulating layer of a printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.
  • the content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.
  • the resin composition of the present invention may contain other components as necessary.
  • other components include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, and resin additives such as dispersants, thickeners, antifoaming agents, leveling agents, and colorants. Etc.
  • the method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounded component is added with a solvent if necessary, and mixed and dispersed using a rotary mixer or the like.
  • the resin composition of the present invention provides a cured product (insulating layer) excellent in both thermal diffusibility and adhesion strength to the metal layer. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and interlayer insulation of the printed wiring board. It can be more suitably used as a resin composition for forming a layer (a resin composition for an interlayer insulating layer of a printed wiring board). In addition, since the resin composition of the present invention exhibits an appropriate melt viscosity and is excellent in component embedding properties, it can be suitably used even when the printed wiring board is a component built-in circuit board.
  • the resin composition of the present invention can be suitably used as a resin composition for embedding components on a component-embedded circuit board (resin composition for embedding components).
  • the resin composition of the present invention also includes a sheet-like laminated material selected from the group consisting of an adhesive film and a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, a component-filling resin, and the like. It can be used in a wide range of applications where the composition is required.
  • the resin composition of the present invention provides a cured product excellent in both thermal diffusibility and adhesion strength to the metal layer, it can be suitably used for adhesion between a semiconductor module and a metal radiator in a power semiconductor device. . Thereby, it is possible to efficiently diffuse the heat generated by the power semiconductor element to the metal radiator.
  • the resin composition of the present invention can be further used for various applications that require high thermal conductivity.
  • the resin composition of the present invention can be applied and used in a varnish state, but industrially, it is generally preferable to use it in the form of an adhesive film.
  • the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is the resin composition of the present invention. Consists of.
  • Examples of the support include a film made of a plastic material, a metal foil, and release paper, and a film made of a plastic material and a metal foil are preferable.
  • plastic material examples include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA).
  • Cyclic polyolefin triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like.
  • TAC triacetyl cellulose
  • PES polyether sulfide
  • polyether ketone polyimide and the like.
  • polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly
  • examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable.
  • a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.
  • the support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer.
  • a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.
  • the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins.
  • Examples of commercially available release agents include “SK-1”, “AL-5”, “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.
  • the thickness of the support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, and more preferably in the range of 10 ⁇ m to 60 ⁇ m.
  • a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.
  • the thickness of the resin composition layer is preferably 200 ⁇ m from the viewpoint of efficiently diffusing heat between the layers (conductor layer-insulating layer-conductor layer, semiconductor module-cured material-metal radiator, etc.), although it depends on the application. Below, more preferably 180 ⁇ m or less, still more preferably 160 ⁇ m or less, 140 ⁇ m or less, or 120 ⁇ m or less.
  • the lower limit of the thickness of the resin composition layer is preferably sufficiently larger than the average particle diameter d c3 ( ⁇ m) of the component (C3). For example, d c3 +45 ( ⁇ m) or more, d c3 +55 ( ⁇ m) ) Or more, d c3 +65 ( ⁇ m) or more.
  • a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied on a support using a die coater or the like and further dried to form a resin composition layer.
  • a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied on a support using a die coater or the like and further dried to form a resin composition layer.
  • organic solvent examples include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc.
  • Carbitols aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone.
  • An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Drying may be performed by a known method such as heating or hot air blowing.
  • the drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less.
  • the resin composition is dried by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes.
  • a physical layer can be formed.
  • the present inventors have found that when the minimum melt viscosity of the resin composition layer is in a specific range, a cured product (insulating layer) that is further excellent in thermal diffusibility and adhesion strength to the metal layer can be obtained.
  • the minimum melt viscosity of the resin composition layer is preferably in the range of 500 poise to 20000 poise.
  • the lower limit of the minimum melt viscosity of the resin composition layer is more preferably 5500 poise or more, further preferably 6000 poise or more, 6500. More than poise or more than 7000 poise.
  • the upper limit of the minimum melt viscosity of the resin composition layer is more preferably 19000 poise or less, still more preferably 18000 poise or less, 17000 poise or less, 16000 poise or less, or 15000 poise or less.
  • the minimum melt viscosity of the resin composition layer is, for example, the content of the component (B), the content of the component (C), the blending ratio of the components (C1) to (C3) in the component (C), and the drying of the resin varnish. It can be adjusted by changing conditions and the like. If the inorganic filler content is increased, the minimum melt viscosity of the resin composition layer may increase excessively. However, in the resin composition of the present invention containing a combination of the above specific (A) to (C) components, ( Even when the content of the component C) is high, a resin composition layer exhibiting a suitable minimum melt viscosity as described above can be obtained.
  • a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support).
  • the thickness of the protective film is not particularly limited, but is, for example, 1 ⁇ m to 40 ⁇ m.
  • the adhesive film of the present invention can be suitably used for applications that require high thermal conductivity. That is, the adhesive film of the present invention can be suitably used as an adhesive film for high heat conduction.
  • the adhesive film of the present invention can provide a cured product having excellent adhesion strength to the metal layer in addition to excellent thermal diffusibility. Therefore, the adhesive film of the present invention can be suitably used for bonding a semiconductor module and a metal radiator in a power semiconductor device.
  • the adhesive film of the present invention provides a cured product (insulating layer) that is excellent in both thermal diffusibility and adhesion strength to the metal layer, so that an insulating layer of a printed wiring board is formed (for an insulating layer of a printed wiring board).
  • an insulating layer of a printed wiring board is formed (for an insulating layer of a printed wiring board).
  • an interlayer insulating layer of a printed wiring board for an interlayer insulating layer of a printed wiring board
  • the adhesive film of the present invention can also be suitably used for embedding components of a component built-in circuit board (for embedding components).
  • the printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
  • the printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned adhesive film.
  • (I) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate
  • (II) A step of thermosetting the resin composition layer to form an insulating layer
  • the lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side.
  • the member that heat-presses the adhesive film to the inner layer substrate include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll).
  • heat-pressing member examples include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll).
  • the lamination of the inner layer substrate and the adhesive film may be performed by a vacuum laminating method.
  • the thermocompression bonding temperature is preferably 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C.
  • the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.
  • the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds.
  • Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.
  • Lamination can be performed with a commercially available vacuum laminator.
  • the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.
  • the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side.
  • the pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate.
  • the smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination
  • step (II) the resin composition layer is thermoset to form an insulating layer.
  • thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.
  • thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably in the range of 170 ° C. to And the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).
  • the resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured.
  • the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower).
  • Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
  • the insulating layer formed from the cured product of the resin composition of the present invention can exhibit sufficient thermal diffusivity.
  • the insulating layer varies depending on the content and type of the inorganic filler in the resin composition to be used, but is preferably 8 W / m ⁇ K or more, more preferably 8.2 W / m ⁇ K or more, and still more preferably.
  • the thermal conductivity of K or more, or 9.0 W / m ⁇ K or more can be exhibited.
  • the upper limit of the thermal conductivity of the insulating layer of the present invention is not particularly limited, but is usually 30 W / m ⁇ K or less.
  • the thermal conductivity of the insulating layer can be measured by known methods such as a heat flow meter method and a temperature wave analysis method. In the present invention, the thermal conductivity of the insulating layer can be measured according to the description of [Measurement of thermal conductivity of cured product] described later.
  • Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer.
  • Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer.
  • the dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.
  • Step (IV) is a step of roughening the insulating layer.
  • the procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed.
  • the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.
  • a swelling liquid An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution.
  • an alkaline solution a sodium hydroxide solution and a potassium hydroxide solution are more preferable.
  • commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd.
  • the swelling treatment with the swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes.
  • a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.
  • an oxidizing agent for example, the alkaline permanganate solution which melt
  • the roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes.
  • the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
  • oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd.
  • the neutralizing solution is preferably an acidic aqueous solution.
  • examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd.
  • the treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes.
  • the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, further preferably 350 nm or less, still more preferably 300 nm or less, 250 nm or less, 200 nm or less. , 150 nm or less, or 100 nm or less.
  • the arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter.
  • a non-contact type surface roughness meter “WYKO NT3300” manufactured by Becoins Instruments is cited.
  • Step (V) is a step of forming a conductor layer.
  • the conductor material used for the conductor layer is not particularly limited.
  • the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal.
  • the conductor layer may be a single metal layer or an alloy layer.
  • the alloy layer for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy).
  • single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / Nickel alloy, copper / titanium alloy layer is preferred, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or nickel / chromium alloy layer is more preferred, aluminum or copper
  • the single metal layer is more preferable.
  • the conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.
  • the thickness of the conductor layer is generally 3 ⁇ m to 35 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, although it depends on the desired printed wiring board design.
  • the insulating layer exhibits good adhesion strength to the conductor layer (metal layer).
  • the adhesion strength between the insulating layer and the conductor layer is preferably 0.5 kgf / cm or more, more preferably 0.55 kgf / cm or more, and further preferably 0.6 kgf / cm. As mentioned above, it is 0.62 kgf / cm or more, 0.64 kgf / cm or more, 0.66 kgf / cm or more, 0.68 kgf / cm or more, or 0.7 kgf / cm or more.
  • the upper limit of the adhesion strength is not particularly limited, but is usually 1.0 kgf / cm or less, 0.9 kgf / cm or less, and the like.
  • the insulating layer exhibits excellent thermal diffusivity, and thus exhibits high adhesion strength to the conductor layer. Therefore, in a semiconductor device in which a semiconductor element is mounted on the printed wiring board, heat generated by the semiconductor element can be efficiently diffused over the entire printed wiring board.
  • the peel strength between the insulating layer and the conductor layer refers to the peel strength (90 degree peel strength) when the conductor layer is peeled in the direction perpendicular to the insulating layer (90 degree direction).
  • the peel strength when peeled in the direction perpendicular to the layer (90-degree direction) can be determined by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.
  • a semiconductor device can be manufactured using the printed wiring board of the present invention.
  • Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, airplanes, and the like).
  • the semiconductor device of the present invention can be manufactured by mounting a semiconductor element on a conductive portion of a printed wiring board.
  • the “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location.
  • the semiconductor element is not particularly limited as long as it is an electric circuit element made of a semiconductor.
  • the semiconductor element mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor element functions effectively.
  • the wire bonding mounting method, the flip chip mounting method, and the bumpless method are used.
  • Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).
  • BBUL build-up layer
  • ACF anisotropic conductive film
  • NCF non-conductive film
  • a mounting method using a build-up layer without a bump means “a mounting method in which a semiconductor element is directly embedded in a recess of a printed wiring board and the semiconductor element is connected to a circuit wiring on the printed wiring board”. That is.
  • the resin composition of the present invention provides a cured product excellent in both thermal diffusibility and adhesion strength to the metal layer. Therefore, the resin composition of the present invention can be advantageously used for forming a thermal diffusion layer in a semiconductor device (power semiconductor device) mounted with a power semiconductor element.
  • FIG. 1 shows a schematic diagram of the power semiconductor device of the present invention according to the above embodiment (wiring with an external circuit is omitted).
  • a power semiconductor device 10 includes a metal radiator 1, a semiconductor module 3, and an insulating layer formed by a cured product of the resin composition of the present invention provided between the metal radiator 1 and the semiconductor module 3. 2 is included.
  • the metal radiator 1 has a first main surface 1a and a second main surface 1b.
  • the metal radiator is not particularly limited as long as it is a radiator made of a metal material, and a known metal radiator that can be used in a power semiconductor device may be used. Aluminum and copper are suitable as the metal material for the metal radiator.
  • the first main surface 1a of the metal radiator 1 may be flat or uneven. Even if the 1st main surface 1a of a metal heat sink is flat, the resin composition of this invention can implement
  • the arithmetic mean roughness (Ra) of the first main surface of the metal radiator may be 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or less, or 50 nm or less.
  • the lower limit of Ra on the first main surface of the metal radiator is not particularly limited, but may be preferably 1 nm or more, 5 nm or more, 10 nm or more, etc. from the viewpoint of stabilizing the adhesion strength between the insulating layer and the metal radiator. .
  • the second main surface 1b of the metal radiator 1 may be flat or uneven. From the viewpoint of efficiently dissipating heat to the external environment, it is preferable that the second main surface of the metal radiator has an uneven shape (not shown) so as to increase the heat dissipation surface area.
  • the metal heat dissipating body 1 may have a heat exchange medium (for example, a coolant such as water) formed therein (not shown) so that heat from the semiconductor module 3 can be efficiently diffused.
  • a heat exchange medium for example, a coolant such as water
  • the semiconductor module 3 includes a semiconductor element substrate 4, a power semiconductor element 8, and lead wires 9 for conducting the semiconductor element substrate and the power semiconductor element.
  • the semiconductor element substrate 4 includes a substrate 6, a metal layer 7 provided on the surface of the substrate on the insulating layer 2 side, and a metal layer (circuit) 5 provided on the surface of the substrate opposite to the insulating layer 2.
  • the substrate 6 may be the same as the “inner layer substrate” in the above [printed wiring board], and may be formed from a cured product of the resin composition of the present invention.
  • the metal layer (circuit) 5 and the metal layer 6 may be the same as the “conductor layer” in the [printed wiring board].
  • the semiconductor element substrate 4 may also be a printed wiring board including an insulating layer formed of a cured product of the resin composition of the present invention.
  • the semiconductor module is not limited to the embodiment shown in FIG. 1, and any semiconductor module including a power semiconductor element may be used without any particular limitation.
  • a semiconductor module including a lead frame and a power semiconductor element mounted on the lead frame may be used as in a power semiconductor device described in Japanese Patent Application Laid-Open No. 2002-246542.
  • the second main surface 3b of the semiconductor module (that is, the surface of the metal layer 7). ) Is flat, good adhesion strength to the semiconductor module can be realized.
  • Ra of the second main surface of the semiconductor module may be the same as Ra of the first main surface of the metal radiator.
  • Ra of at least one of the first main surface of the metal radiator and the second main surface of the semiconductor module may be 500 nm or less.
  • the insulating layer formed from the cured product of the resin composition of the present invention is excellent in both thermal diffusibility and adhesion strength to the metal layer.
  • the thermal conductivity of the insulating layer is 8 W / m ⁇ K or more
  • the adhesion strength between the insulating layer and at least one of the first main surface of the metal radiator and the second main surface of the semiconductor module is 0.5 kgf / cm or more.
  • the preferable range of the thermal conductivity of the insulating layer is as described for the insulating layer of the [printed wiring board], and the insulating layer, the first main surface of the metal radiator, and the second of the semiconductor module.
  • the adhesion strength with at least one of the main surfaces of the printed wiring board can be the same as the adhesion strength between the insulating layer and the conductor layer of the [printed wiring board].
  • a sealing resin (not shown) for sealing the semiconductor module may be provided in order to protect the power semiconductor element from deterioration due to the environment such as light, heat, and humidity.
  • the sealing resin a known resin that can be used in the manufacture of a semiconductor device may be used, or the resin composition of the present invention may be used. Therefore, in one embodiment, the power semiconductor device of the present invention includes a sealing layer formed of a cured product of the resin composition of the present invention provided to seal the semiconductor module.
  • the present invention also provides a laminate of an insulating layer and a metal layer.
  • the laminate of the present invention is a laminate of an insulating layer and a metal layer, the thermal conductivity of the insulating layer is 8 W / m ⁇ K or more, and the adhesion strength between the insulating layer and the metal layer is 0.5 kgf. / Cm or more.
  • the laminate of the present invention including an insulating layer excellent in both thermal diffusibility and adhesion strength to a metal layer is realized for the first time using the resin composition of the present invention. That is, the laminated body of this invention contains the insulating layer and metal layer which were formed with the hardened
  • the preferable range of the thermal conductivity of the insulating layer and the preferable range of the adhesion strength between the insulating layer and the metal layer are as described in the above [Printed wiring board].
  • the metal layer may be the same as the “conductor layer” in the above [printed wiring board].
  • the metal layer may be the same as the “metal radiator” in the above [power semiconductor device]. Therefore, in the laminate of the present invention, the metal layer is preferably made of copper or aluminum.
  • the thickness of the insulating layer may be the same as the preferred thickness of the resin composition layer in [Adhesive film].
  • an insulating layer having a desired thickness may be achieved by laminating resin composition layers using a plurality of adhesive films. .
  • the support is peeled off, and an electrolytic copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd.) is attached so that the resin composition layer and the glossy surface of the electrolytic copper foil are bonded to the exposed surface of the resin composition layer.
  • JTCP-35u ”and Ra of glossy surface: 200 nm were laminated.
  • pressing was performed at 140 ° C. and a pressure of 5 kgf / cm 2 for 10 minutes, then at 200 ° C. and a pressure of 5 kgf / cm 2 for 90 minutes, The resin composition layer was cured to form an insulating layer.
  • melt viscosity was measured using a dynamic viscoelasticity measuring device (“Reosol-G3000” manufactured by UBM Co., Ltd.). About 1.8 g of the sample resin composition, using a parallel plate having a diameter of 18 mm, the temperature was increased from a measurement start temperature of 60 ° C. at a temperature increase rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz The measurement was performed under a measurement condition of 1 deg strain. The lowest viscosity value ( ⁇ ) was taken as the lowest melt viscosity.
  • a phosphoric acid ester type anionic surfactant (“RS-610” manufactured by Toho Chemical Industry Co., Ltd.)
  • aluminum nitride having an average particle diameter of 1.1 ⁇ m (manufactured by Tokuyama Co., Ltd.) “Shape H”, specific surface area 2.5 m 2 / g, specific gravity 3.0 g / cm 3 , hereinafter referred to as “aluminum nitride 1”) 34 parts, average particle size 4.7 ⁇ m aluminum nitride (“Shapal” manufactured by Tokuyama Corporation) H ”, specific surface area 1.0 m 2 / g, specific gravity 3.1 g / cm 3 , hereinafter referred to as“ aluminum nitride 2 ”) 34 parts, average particle diameter 22.3 ⁇ m of aluminum nitride (“ Shapal H ”manufactured by Tokuyama Corporation) ”, Specific surface area of 0.2 m 2 / g, specific gravity
  • phenoxy resin (YL7553” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of methyl ethyl ketone (MEK) and cyclohexanone having a solid content of 30% by mass)
  • liquid phenolic curing agent at least allyl group and alkyl Liquid phenol having a group
  • ACG-1 manufactured by Gunei Chemical Industry Co., Ltd., 5.5 equivalents of a hydroxyl group, weight average molecular weight 1690
  • curing accelerator (4-dimethylaminopyridine (DMAP), solid content
  • a resin varnish was prepared by mixing 4.5 parts of a 5 mass% MEK solution).
  • PET film with a release layer (“PET501010” manufactured by Lintec Corporation, thickness 50 ⁇ m) was prepared as a support.
  • a resin varnish is uniformly applied on the release layer side of the support so that the thickness of the resin composition layer after drying is 100 ⁇ m, and dried at 75 ° C. to 120 ° C. for 10 minutes to produce an adhesive film. did.
  • Example 2 Example 1 except that 2 parts of carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., solid content 51%, viscosity 38 mPa ⁇ s (20 ° C.)) was further added after kneading with 3 rolls. An adhesive film was prepared in the same manner.
  • V-03 manufactured by Nisshinbo Chemical Co., Ltd., solid content 51%, viscosity 38 mPa ⁇ s (20 ° C.)
  • Example 3 An adhesive film was produced in the same manner as in Example 1 except that the amount of aluminum nitride 1 was changed to 17 parts and the amount of aluminum nitride 2 was changed to 51 parts.
  • Example 6 Adhesive film in the same manner as in Example 1 except that the amount of aluminum nitride 1 was changed to 72.5 parts, the amount of aluminum nitride 2 was changed to 14.5 parts, and the amount of aluminum nitride 3 was changed to 116 parts.
  • the amount of aluminum nitride 1 was changed to 72.5 parts
  • the amount of aluminum nitride 2 was changed to 14.5 parts
  • the amount of aluminum nitride 3 was changed to 116 parts.
  • Example 7 Adhesive film in the same manner as in Example 1 except that the amount of aluminum nitride 1 was changed to 38.1 parts, the amount of aluminum nitride 2 was changed to 38.1 parts, and the amount of aluminum nitride 3 was changed to 127 parts. Was made.
  • Example 8 Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169), 5 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts of “NC3000L”, epoxy equivalent of about 269), 3 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) are dissolved in 10 parts of solvent naphtha with stirring while heating. It was.
  • a phosphate ester type anionic surfactant (“RS-710” manufactured by Toho Chemical Industry Co., Ltd.)
  • aluminum nitride having an average particle size of 1.5 ⁇ m (manufactured by Tokuyama Co., Ltd.) "Shape H (water-resistant treated product)", specific surface area 2.5 m 2 / g, specific gravity 3.3 g / cm 3 , hereinafter referred to as “aluminum nitride 4”) 34 parts, average particle size 5.2 ⁇ m aluminum nitride (stock ) "Shapal H (water-resistant treated product)" manufactured by Tokuyama, specific surface area 0.8 m 2 / g, specific gravity 3.3 g / cm 3 , hereinafter referred to as “aluminum nitride 5”) 34 parts, nitriding with an average particle diameter of 23.0 ⁇ m
  • aluminum nitride 5 nitriding with an average particle diameter of 23.0 ⁇
  • Example 9 An adhesive film was prepared in the same manner as in Example 8 except that the liquid phenolic curing agent was changed to 5.5 parts “MEH-8000H” (liquid phenol having an allyl group, hydroxyl equivalent weight of about 140) manufactured by Meiwa Kasei Co., Ltd. Produced.
  • MEH-8000H liquid phenol having an allyl group, hydroxyl equivalent weight of about 140
  • Example 10 The compounding amount of aluminum nitride 4 is 17.0 parts, the compounding amount of aluminum nitride 5 is 51.0 parts, and the curing accelerator is tetrabutylphosphonium decanoate (TBPDA) (MEK solution having a solid content of 10% by mass).
  • TPDA tetrabutylphosphonium decanoate
  • the adhesive film was produced like Example 8 except having changed into the part.
  • Example 11 The amount of aluminum nitride 4 was changed to 37.8 parts, and the amount of aluminum nitride 5 was changed to 37.8 parts. Instead of aluminum nitride 6, aluminum nitride having an average particle diameter of 30 ⁇ m (“Shapal H” manufactured by Tokuyama Corporation) was used.
  • Example 12 The amount of phosphate ester type anionic surfactant is 1.2 parts, the amount of aluminum nitride 4 is 44.4 parts, and alumina with an average particle diameter of 4 ⁇ m is used instead of aluminum nitride 5 (manufactured by Showa Denko KK) “CB-P05”, specific surface area 0.7 m 2 / g, specific gravity 2.2 g / cm 3 , hereinafter referred to as “alumina 2”) 44.4 parts, instead of aluminum nitride 6, alumina having an average particle diameter of 28 ⁇ m (Showa "CB-A30S” manufactured by Denko Co., Ltd., with a specific surface area of 0.2 m 2 / g, specific gravity of 2.3 g / cm 3 (hereinafter referred to as “alumina 3”) was added and 148 parts were added, and the phenoxy resin was changed to “YL7482.” An adhesive film was produced in the same manner as in Example 8 except that.
  • Example 13 The amount of the phosphate ester type anionic surfactant was changed to 1.1 parts.
  • alumina having an average particle diameter of 1 ⁇ m (“AHP300” manufactured by Nippon Light Metal Co., Ltd., specific surface area 2.6 m 2 / g, specific gravity 3.98 g / cm 3 , hereinafter referred to as “alumina 1”)
  • 40.8 parts was added, the amount of alumina 2 was changed to 40.8 parts, and aluminum nitride 7 was replaced with 136 instead of alumina 3.
  • An adhesive film was produced in the same manner as in Example 12 except that the curing accelerator was changed to 6 parts of tetrabutylphosphonium decanoate (TBPDA) (MEK solution having a solid content of 10% by mass).
  • TPDA tetrabutylphosphonium decanoate
  • Example 14 An adhesive film was produced in the same manner as in Example 13 except that the curing accelerator was changed to 4.5 parts of 4-dimethylaminopyridine (DMAP) and MEK solution having a solid content of 5% by mass.
  • DMAP 4-dimethylaminopyridine

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Abstract

L'invention concerne une composition de résine qui donne des objets durcis qui présentent des propriétés de diffusion de chaleur suffisantes et qui ont une force satisfaisante d'adhérence à des couches métalliques. La composition de résine comprend (A) une résine époxyde, (B) un agent de durcissement, et (C) des charges minérales. Le constituant (B) comprend un agent de durcissement phénolique liquide et le constituant (C) comprend une charge minérale (C1) ayant un diamètre moyen de particule de 0,1 µm ou plus mais inférieur à 3 µm, une charge minérale (C2) ayant un diamètre moyen de particule de 3 µm ou plus mais inférieur à 10 µm, et une charge minérale (C3) ayant un diamètre moyen de particule de 10 à 35 µm.
PCT/JP2016/052394 2015-02-05 2016-01-27 Composition de résine WO2016125664A1 (fr)

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JP2018049878A (ja) * 2016-09-20 2018-03-29 トヨタ自動車株式会社 半導体装置
KR20180035164A (ko) * 2016-09-28 2018-04-05 아지노모토 가부시키가이샤 수지 조성물
KR20180108482A (ko) * 2017-03-23 2018-10-04 아지노모토 가부시키가이샤 수지 조성물
WO2019078044A1 (fr) * 2017-10-18 2019-04-25 株式会社スリーボンド Composition de résine thermoconductrice, objet durci, et procédé de rayonnement thermique
WO2019106953A1 (fr) * 2017-11-30 2019-06-06 京セラ株式会社 Feuille de résine, dispositif à semi-conducteurs et procédé de fabrication d'un dispositif à semi-conducteurs
JP2019179835A (ja) * 2018-03-30 2019-10-17 住友ベークライト株式会社 放熱絶縁シート、および半導体装置
WO2020067364A1 (fr) * 2018-09-28 2020-04-02 富士フイルム株式会社 Composition pour former des matériaux thermoconducteurs, matériau thermoconducteur, feuille thermoconductrice, dispositif avec couche thermoconductrice, et film
JP6692512B1 (ja) * 2018-12-25 2020-05-13 富士高分子工業株式会社 熱伝導組成物及びこれを用いた熱伝導性シート
WO2020137086A1 (fr) * 2018-12-25 2020-07-02 富士高分子工業株式会社 Composition thermoconductrice et feuille thermoconductrice l'utilisant
WO2020188641A1 (fr) * 2019-03-15 2020-09-24 日立化成株式会社 Composition de résine époxy, dispositif de composant électronique et procédé de fabrication de dispositif de composant électronique
WO2022113941A1 (fr) * 2020-11-30 2022-06-02 株式会社トクヤマ Composition de résine
WO2023181905A1 (fr) * 2022-03-22 2023-09-28 日本発條株式会社 Procédé de fabrication de stratifié

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CN110577722A (zh) * 2019-09-12 2019-12-17 江苏硕阳电子科技有限公司 一种混合有环氧树脂的用于空心电抗器的导热绝缘材料及其制备方法
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