WO2013065759A1 - エポキシ樹脂組成物、半硬化エポキシ樹脂組成物、硬化エポキシ樹脂組成物、樹脂シート、プリプレグ、積層板、金属基板、配線板、半硬化エポキシ樹脂組成物の製造方法及び硬化エポキシ樹脂組成物の製造方法 - Google Patents

エポキシ樹脂組成物、半硬化エポキシ樹脂組成物、硬化エポキシ樹脂組成物、樹脂シート、プリプレグ、積層板、金属基板、配線板、半硬化エポキシ樹脂組成物の製造方法及び硬化エポキシ樹脂組成物の製造方法 Download PDF

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Publication number
WO2013065759A1
WO2013065759A1 PCT/JP2012/078240 JP2012078240W WO2013065759A1 WO 2013065759 A1 WO2013065759 A1 WO 2013065759A1 JP 2012078240 W JP2012078240 W JP 2012078240W WO 2013065759 A1 WO2013065759 A1 WO 2013065759A1
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WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
group
iii
cured
Prior art date
Application number
PCT/JP2012/078240
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English (en)
French (fr)
Japanese (ja)
Inventor
優香 吉田
竹澤　由高
高橋　裕之
靖夫 宮崎
Original Assignee
日立化成株式会社
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Priority claimed from PCT/JP2011/075345 external-priority patent/WO2013065159A1/ja
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to KR1020147013361A priority Critical patent/KR20140099870A/ko
Priority to JP2013541829A priority patent/JP6119610B2/ja
Priority to CN201280053406.5A priority patent/CN103906785A/zh
Publication of WO2013065759A1 publication Critical patent/WO2013065759A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
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    • 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
    • B32B15/043—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 metal
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    • 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
    • B32B15/092—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 comprising epoxy resins
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1009—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using vacuum and fluid pressure
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • 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
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    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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Definitions

  • the present invention relates to an epoxy resin composition, a semi-cured epoxy resin composition, a cured epoxy resin composition, a resin sheet, a prepreg, a laminate, a metal substrate, a wiring board, a method for producing a semi-cured epoxy resin composition, and a cured epoxy resin composition.
  • the present invention relates to a method for manufacturing a product.
  • a cured resin made of a thermosetting resin composition is widely used from the viewpoint of insulation and heat resistance.
  • the thermal conductivity of the cured resin is generally low and is a major factor hindering heat dissipation, development of a cured resin having high thermal conductivity is desired.
  • a cured product of an epoxy resin composition having a mesogenic skeleton in the molecular structure As a cured resin having high thermal conductivity, a cured product of an epoxy resin composition having a mesogenic skeleton in the molecular structure has been proposed (see, for example, Japanese Patent No. 4118691).
  • the epoxy resin having a mesogen skeleton in the molecular structure include compounds disclosed in Japanese Patent No. 4619770, Japanese Patent Application Laid-Open No. 2011-74366, Japanese Patent Application Laid-Open No. 2011-84557, and the like.
  • a technique for achieving high thermal conductivity of the resin cured product there is a method of filling a resin composition with a thermal conductive filler made of high thermal conductive ceramic to form a composite material.
  • a thermal conductive filler made of high thermal conductive ceramic to form a composite material.
  • high thermal conductive ceramics alumina, boron nitride, aluminum nitride, silica, silicon nitride, magnesium oxide, silicon carbide and the like are known.
  • the composite material can achieve both high thermal conductivity and electrical insulation.
  • a resin composition containing a so-called mesogen skeleton-containing epoxy resin having a biphenyl skeleton, a phenol resin, and spherical alumina as essential components has been disclosed (see, for example, Japanese Patent No. 2874089), and a semiconductor encapsulation excellent in high thermal conductivity is disclosed. It is reported that it is a resin composition for stopping. Also disclosed is a resin composition containing an epoxy resin having a biphenyl skeleton, a curing agent having a xanthene skeleton, and an inorganic filler (see, for example, JP-A-2007-262398). It is said that there is.
  • a resin composition containing a tricyclic mesogen skeleton-containing epoxy resin, a curing agent, and alumina powder is disclosed (see, for example, JP-A-2008-13759), and has a high thermal conductivity and excellent workability. Has been.
  • Epoxy resin monomers having a mesogen skeleton in the molecular structure are known as thermosetting resins having high thermal conductivity, but the high thermal conductivity of the cured resin obtained by the combined curing agent varies greatly.
  • the epoxy resin monomer forms a high-order structure having high orderness, which contributes to high thermal conductivity.
  • a high-order structure cannot be formed, and high thermal conductivity cannot be obtained. . That is, in order to obtain a cured resin having high thermal conductivity, it is important to select both the thermosetting resin and the curing agent.
  • high heat resistance has recently been demanded for insulating materials for heat dissipation applications.
  • the present invention provides an epoxy resin composition, a semi-cured epoxy resin composition and a cured epoxy resin composition that can form a cured product having high thermal conductivity and high heat resistance, and a method for producing the same. Is an issue. It is another object of the present invention to provide a resin sheet, a prepreg, a laminate, a metal substrate, and a wiring board that are configured using the epoxy resin composition and have high thermal conductivity and high heat resistance.
  • the present invention includes the following aspects.
  • An epoxy resin composition comprising an epoxy resin monomer represented by the following general formula (I), a curing agent containing a novolak resin obtained by novolacizing a divalent phenol compound, and an alumina filler containing ⁇ -alumina. It is a thing.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the curing agent is a novolak resin including a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (II-1) and (II-2) ⁇ 1> It is an epoxy resin composition as described in above.
  • R 21 and R 24 each independently represents an alkyl group, an aryl group or an aralkyl group.
  • R 22 , R 23 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
  • m21 and m22 each independently represents an integer of 0-2.
  • n21 and n22 each independently represents an integer of 1 to 7.
  • the curing agent is a novolak resin including a compound having a structure represented by at least one selected from the group consisting of the following general formulas (III-1) to (III-4): It is an epoxy resin composition of description.
  • n31 to n34 each independently represent a positive integer.
  • Ar 31 to Ar 34 each independently represent either a group represented by the following general formula (III-a) or a group represented by the following general formula (III-b).
  • R 31 and R 34 each independently represent a hydrogen atom or a hydroxyl group.
  • R 32 and R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • ⁇ 5> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the alumina filler is 60% to 90% by volume in the entire volume.
  • R 41 , R 42 and R 43 each independently represent a linear or branched alkyl group or a hydrogen atom.
  • R 44 represents a linear or branched alkyl group.
  • n4 represents an arbitrary integer.
  • the said elastomer is an epoxy resin composition as described in ⁇ 6> containing the acrylic elastomer containing the structural unit represented by the following general formula (V).
  • R 51 and R 52 each independently represent a linear or branched alkyl group having a different carbon number.
  • R 53 to R 56 each independently represents a hydrogen atom or a methyl group.
  • a semi-cured epoxy resin composition that is a semi-cured product of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • a cured epoxy resin composition that is a cured product of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • a resin sheet which is a sheet-like molded body of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 12> an adherend, an epoxy resin composition according to any one of ⁇ 1> to ⁇ 7>, a resin sheet according to ⁇ 10>, and ⁇ 11>, which is disposed on the adherend
  • a laminate having a semi-cured epoxy resin composition layer that is at least one semi-cured material selected from the group consisting of the prepregs described in 1. or a cured epoxy resin composition layer that is a cured material.
  • ⁇ 13> selected from the group consisting of metal foil, the epoxy resin composition according to any one of ⁇ 1> to ⁇ 7>, the resin sheet according to ⁇ 10>, and the prepreg according to ⁇ 11>.
  • ⁇ 14> selected from the group consisting of a metal plate, the epoxy resin composition according to any one of ⁇ 1> to ⁇ 7>, the resin sheet according to ⁇ 10>, and the prepreg according to ⁇ 11>.
  • a method for producing a semi-cured epoxy resin composition comprising a step of forming an epoxy resin layer on a material and a step of heat-treating the epoxy resin layer to form a semi-cured epoxy resin layer.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the curing agent is a novolac resin containing a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (II-1) and (II-2) ⁇ 15>
  • the manufacturing method of the semi-hardened epoxy resin composition as described in any one of.
  • R 21 and R 24 each independently represents an alkyl group, an aryl group or an aralkyl group.
  • R 22 , R 23 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
  • m21 and m22 each independently represents an integer of 0-2.
  • n21 and n22 each independently represents an integer of 1 to 7.
  • the curing agent is a novolak resin including a compound having a structure represented by at least one selected from the group consisting of the following general formulas (III-1) to (III-4): It is a manufacturing method of the semi-hardened epoxy resin composition of description.
  • n31 to n34 each independently represent a positive integer.
  • Ar 31 to Ar 34 each independently represent either a group represented by the following general formula (III-a) or a group represented by the following general formula (III-b).
  • R 31 and R 34 each independently represent a hydrogen atom or a hydroxyl group.
  • R 32 and R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • a step of forming an epoxy resin layer on the material, a step of heat-treating the epoxy resin layer to form a semi-cured epoxy resin layer, a heat-treated epoxy resin layer of the semi-cured epoxy resin layer, and a cured epoxy resin layer A process for producing a cured epoxy resin composition.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the curing agent is a novolak resin containing a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (II-1) and (II-2) ⁇ 18> It is a manufacturing method of the cured epoxy resin composition as described in above.
  • R 21 and R 24 each independently represents an alkyl group, an aryl group or an aralkyl group.
  • R 22 , R 23 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
  • m21 and m22 each independently represents an integer of 0-2.
  • n21 and n22 each independently represents an integer of 1 to 7.
  • the curing agent is a novolak resin including a compound having a structure represented by at least one selected from the group consisting of the following general formulas (III-1) to (III-4): It is a manufacturing method of described hardening epoxy resin composition.
  • n31 to n34 each independently represent a positive integer.
  • Ar 31 to Ar 34 each independently represent either a group represented by the following general formula (III-a) or a group represented by the following general formula (III-b).
  • R 31 and R 34 each independently represent a hydrogen atom or a hydroxyl group.
  • R 32 and R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • a semiconductor module in which a metal plate, a solder layer, and a semiconductor chip are laminated in this order, a heat radiating member, and ⁇ 1> to ⁇ 7> disposed between the metal plate and the heat radiating member of the semiconductor module. And a cured product of the epoxy resin composition according to any one of the above.
  • an epoxy resin composition a semi-cured epoxy resin composition and a cured epoxy resin composition capable of forming a cured product having high thermal conductivity and high heat resistance, and a method for producing the same.
  • a resin sheet, a prepreg, a laminate, a metal substrate, and a wiring board that are configured using the epoxy resin composition and have high thermal conductivity and high heat resistance can be provided.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • the epoxy resin composition of the present invention contains an epoxy resin monomer represented by the following general formula (I), a curing agent containing a resin in which a divalent phenol compound is novolakized, and an alumina filler containing ⁇ -alumina. To do.
  • the epoxy resin composition may further contain other components as necessary. With this configuration, the epoxy resin composition of the present invention can exhibit excellent high thermal conductivity and high heat resistance after curing. Furthermore, the epoxy resin composition of the present invention exhibits excellent moldability.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the epoxy resin monomer represented by the above general formula (I) is an epoxy resin monomer having a mesogenic group in the molecular structure. It is described in Japanese Patent No. 4118691 that a cured product of an epoxy resin monomer having a mesogenic group in the molecular structure is excellent in thermal conductivity. However, by combining the epoxy resin monomer represented by the general formula (I) with a novolak resin in which a divalent phenol compound is novolaked, the heat of the cured epoxy resin composition cannot be predicted from the description of Japanese Patent No. 4118691. Conductivity is improved and heat resistance is also improved. This is considered to be because, for example, a very high-density crosslink is formed in the cured product composed of the epoxy resin monomer and the novolak resin. Generally, when the crosslink density is high, the glass transition temperature (Tg) of the cured body is increased, and when the Tg of the cured body is increased, the thermal conductivity and heat resistance tend to be improved.
  • Tg glass transition temperature
  • the mesogenic group refers to a functional group that facilitates the expression of crystallinity or liquid crystallinity by the action of intermolecular interaction.
  • Specific examples include a biphenyl group, a phenylbenzoate group, an azobenzene group, a stilbene group, and derivatives thereof.
  • the epoxy resin monomer represented by the general formula (I) is also a kind of epoxy resin monomer having a mesogenic group in the molecular structure.
  • the present inventors have formed a higher order structure having higher ordering with an ⁇ -alumina filler as a center, the epoxy resin monomer represented by the general formula (I) having a mesogenic group in the molecular structure, It has been found that the thermal conductivity of the cured product is dramatically improved. That is, since the cured product of the epoxy resin monomer serves as a heat conduction path between the ⁇ -alumina fillers, higher heat conductivity can be achieved. Also in the cured epoxy resin composition obtained by curing the epoxy resin composition of the present invention, the epoxy resin monomer represented by the general formula (I) forms a higher-order structure having higher orderness centering on the ⁇ -alumina filler. Demonstrates excellent thermal conductivity.
  • the higher order structure means a structure including a higher order structure in which the constituent elements are arranged to form a micro ordered structure, and corresponds to, for example, a crystal phase or a liquid crystal phase.
  • the presence confirmation of such a higher-order structure can be easily determined by observation with a polarizing microscope. In other words, in the observation in the crossed Nicols state, it can be determined by seeing interference fringes due to depolarization.
  • This higher-order structure usually exists in an island shape in the cured epoxy resin composition to form a domain structure, and one of the islands corresponds to one higher-order structure.
  • the constituent elements of this higher order structure are generally formed by covalent bonds.
  • the presence of a higher order structure in the cured epoxy resin composition containing an ⁇ -alumina filler can be confirmed as follows. Cured product of a composition obtained by adding 5% to 10% by volume of ⁇ -alumina filler to the epoxy resin monomer represented by the general formula (I) having a mesogenic group in the molecular structure and a curing agent (thickness: 0.1 ⁇ m to 20 ⁇ m) is prepared. Observation is performed using a polarizing microscope (for example, Olympus BX51) in a state where the obtained cured body is sandwiched between slide glasses (thickness: about 1 mm).
  • a polarizing microscope for example, Olympus BX51
  • the resin forms a higher-order structure depending on whether an interference pattern is observed or a dark field is observed in observation in a crossed Nicol state. It can be determined whether or not.
  • the dark field region where no interference pattern is observed is because the resin does not form a higher order structure. It is impossible to determine whether it is a thing. Therefore, it is necessary to observe the analyzer with the analyzer rotated by 60 ° with respect to the polarizer.
  • the alumina filler becomes a dark field regardless of the angle between the polarizer and the analyzer, but the portion where the resin does not form a higher order structure is observed with the analyzer rotated 60 ° relative to the polarizer. It is not a dark field, but a little light is transmitted and it looks bright. That is, it is possible to distinguish between a portion where the resin does not form a higher order structure and one derived from an alumina filler.
  • a combination of the epoxy resin monomer represented by the above general formula (I), a resin obtained by novolacizing a divalent phenol compound, and an ⁇ -alumina filler makes it possible to cure with high thermal conductivity and high heat resistance.
  • An epoxy resin composition capable of forming a body is obtained.
  • a resin sheet and a prepreg configured using the epoxy resin composition, and further, a laminated board, a metal substrate, and a wiring board provided with an insulating layer obtained by curing the epoxy resin composition have higher thermal conductivity and higher Demonstrate heat resistance.
  • the material used for the epoxy resin composition and the physical properties of the epoxy resin composition will be described.
  • epoxy resin monomer contains at least 1 sort (s) of the epoxy resin monomer represented by the following general formula (I).
  • the epoxy resin monomer represented by the general formula (I) tends to form a higher order structure having higher ordering with ⁇ -alumina as the center. As a result, the thermal conductivity after curing tends to improve dramatically. This is considered to be because the presence of ⁇ -alumina makes the cured epoxy resin body having a higher order structure an efficient heat conduction path and provides high heat conductivity.
  • the epoxy resin monomer represented by the general formula (I) has a high transition temperature to the liquid crystal phase, that is, a melting temperature of 150 ° C. Therefore, when the epoxy resin monomer is to be melted, the curing reaction generally proceeds simultaneously with melting, depending on the curing agent and the curing catalyst used. As a result, the epoxy resin monomer becomes a cured body before forming a higher order structure. However, in a system containing ⁇ -alumina, a cured product in which the epoxy resin monomer forms a higher order structure tends to be obtained even when heated at a high temperature.
  • the epoxy resin monomer represented by the general formula (I) can only exhibit a nematic structure with the epoxy resin monomer alone. For this reason, it is relatively difficult to form a higher order structure in an epoxy resin monomer having a mesogenic group in the molecular structure.
  • the epoxy resin monomer represented by the general formula (I) exhibits a smectic structure having a higher order than the nematic structure. As a result, the thermal conductivity is unpredictably high from a cured product composed of a single epoxy resin monomer.
  • each of the nematic structure and the smectic structure is a kind of liquid crystal structure.
  • the nematic structure is a liquid crystal structure in which the molecular long axis is oriented in a uniform direction and has only alignment order.
  • the smectic structure is a liquid crystal structure having a one-dimensional positional order in addition to the orientation order and having a layer structure. The order is higher in the smectic structure than in the nematic structure. For this reason, the thermal conductivity of the cured resin is also higher when it exhibits a smectic structure.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, It is more preferably an atom or a methyl group, and further preferably a hydrogen atom. Further, 2 to 4 of R 1 to R 4 are preferably hydrogen atoms, 3 or 4 are preferably hydrogen atoms, and all 4 are preferably hydrogen atoms. When any of R 1 to R 4 is an alkyl group having 1 to 3 carbon atoms, at least one of R 1 and R 4 is preferably an alkyl group having 1 to 3 carbon atoms.
  • the epoxy resin monomer includes 4- ⁇ 4- (2,3-epoxypropoxy) phenyl ⁇ cyclohexyl-4- (2,3-epoxypropoxy) benzoate and 4- ⁇ 4- (2,3- Epoxypropoxy) phenyl ⁇ cyclohexyl-4- (2,3-epoxypropoxy) -3-methylbenzoate is preferred.
  • the epoxy resin monomer may be used as a prepolymer obtained by partially reacting the epoxy resin monomer with a curing agent described later.
  • Epoxy resin monomers having a mesogenic group in the molecular structure are generally easily crystallized, and the solubility in solvents is often lower than that of general epoxy resin monomers.
  • the epoxy resin monomer represented by the general formula (I) also corresponds to this. However, since the crystallization can be suppressed by partially polymerizing the epoxy resin monomer represented by the general formula (I), the solubility in a solvent is improved, and the moldability may be further improved.
  • the epoxy resin monomer is preferably contained in an amount of 10% by volume to 40% by volume in the total volume of the total solid content of the epoxy resin composition from the viewpoint of moldability, adhesiveness and thermal conductivity, and 15% by volume. More preferably, it is contained in an amount of ⁇ 35% by volume, and more preferably 15% by volume to 30% by volume.
  • the said epoxy resin composition contains the below-mentioned hardening
  • curing agents and hardening accelerator is included in the content rate of an epoxy resin monomer here unless there is particular notice.
  • curing agent and hardening accelerator in this specification be the value calculated
  • the content rate (volume%) of the material used for the epoxy resin composition is a value obtained based on this method.
  • each variable is as follows.
  • Aw mass composition ratio of epoxy resin monomer (mass%)
  • Bw mass composition ratio (% by mass) of curing agent
  • Cw mass composition ratio (mass%) of curing accelerator (optional component)
  • Dw mass composition ratio of alumina filler (mass%)
  • Ew Mass composition ratio (% by mass) of other optional components (excluding organic solvents)
  • Ad Specific gravity of epoxy resin monomer
  • Bd Specific gravity of curing agent
  • Cd Specific gravity of curing accelerator (optional component)
  • Dd Specific gravity of alumina filler
  • Ed Specific gravity of other optional components (excluding organic solvent)
  • the epoxy resin composition includes a curing agent including a novolak resin obtained by novolacizing a divalent phenol compound (hereinafter sometimes referred to as “specific novolak resin”).
  • divalent phenol compound examples include catechol, resorcinol, hydroquinone, 1,2-naphthalenediol, 1,3-naphthalenediol, and the like.
  • a novolak resin obtained by novolacizing a divalent phenol compound refers to a novolak resin in which these compounds are connected by a methylene chain.
  • the thermal conductivity of the epoxy resin composition is improved by using a divalent phenol compound, and the heat resistance is further improved by making these compounds novolak.
  • the specific novolac resin preferably contains a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (II-1) and (II-2).
  • R 21 and R 24 each independently represents an alkyl group, an aryl group or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group represented by R 21 or R 24 may further have a substituent, if possible. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroxyl group.
  • R 21 and R 24 each independently represents an alkyl group, an aryl group or an aralkyl group, and is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms.
  • An alkyl group having 1 to 6 carbon atoms is more preferable.
  • m21 and m22 each independently represents an integer of 0-2. If m21 is 2, two R 21 may be the same or different and when m22 is 2, two R 24 may be different even in the same.
  • m21 and m22 are each independently preferably 0 or 1, and more preferably 0.
  • N21 and n22 each independently represents an integer of 1 to 7, and the content of the structural unit represented by the general formula (II-1) or the structural unit represented by the general formula (II-2) Show.
  • R 22 , R 23 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group represented by R 22 , R 23 , R 25 or R 26 may further have a substituent, if possible. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroxyl group.
  • R 22 , R 23 , R 25 and R 26 in the present invention are preferably a hydrogen atom, an alkyl group, or an aryl group from the viewpoints of storage stability and thermal conductivity. It is more preferably a 4 alkyl group or an aryl group having 6 to 12 carbon atoms, and further preferably a hydrogen atom. Furthermore, from the viewpoint of heat resistance, at least one of R 22 and R 23 or at least one of R 25 and R 26 is also preferably an aryl group, and more preferably an aryl group having 6 to 12 carbon atoms. .
  • the aryl group may include a hetero atom in the aromatic group, and is preferably a heteroaryl group in which the total number of hetero atoms and carbon is 6 to 12.
  • the curing agent may contain one type of compound having the structural unit represented by the general formula (II-1) or the structural unit represented by the general formula (II-2). It may contain more than species. From the viewpoint of thermal conductivity, the curing agent preferably contains at least a compound having a structural unit represented by the general formula (II-1).
  • the structure represented by the general formula (II-1) is derived from resorcinol. More preferably, it contains at least a compound having a unit.
  • the compound having the structural unit represented by the general formula (II-1) may further contain at least one partial structure derived from a phenol compound other than resorcinol.
  • a phenol compound other than resorcinol examples include phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,3,5. -Trihydroxybenzene and the like.
  • the compound having the structural unit represented by the general formula (II-1) may contain a partial structure derived from these phenol compounds alone or in combination of two or more.
  • the compound represented by the above general formula (II-2) and having a structural unit derived from catechol may contain at least one partial structure derived from a phenol compound other than catechol.
  • the partial structure derived from the phenol compound means a monovalent or divalent group constituted by removing one or two hydrogen atoms from the aromatic ring portion of the phenol compound.
  • the position where the hydrogen atom is removed is not particularly limited.
  • the partial structure derived from a phenol compound other than resorcinol includes phenol, cresol, catechol from the viewpoint of thermal conductivity, adhesiveness, and storage stability.
  • the content ratio of the partial structure derived from resorcinol is not particularly limited. From the viewpoint of the elastic modulus, the content ratio of the partial structure derived from resorcinol to the total mass of the compound having the structural unit represented by the general formula (II-1) is preferably 55% by mass or more, From the viewpoint of the expansion coefficient, it is more preferably 60% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more from the viewpoint of thermal conductivity.
  • the specific novolak resin is more preferably a novolak resin containing a compound having a structure represented by at least one selected from the group consisting of the following general formulas (III-1) to (III-4).
  • n31 to n34 each independently represent a positive integer.
  • Ar 31 to Ar 34 each independently represent either a group represented by the following general formula (III-a) or a group represented by the following general formula (III-b).
  • R 31 and R 34 each independently represent a hydrogen atom or a hydroxyl group.
  • R 32 and R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the curing agent having a structure represented by at least one selected from the group consisting of the above general formulas (III-1) to (III-4) is produced by a production method described later in which a divalent phenol compound is novolakized. It can be generated as a by-product.
  • the structure represented by at least one selected from the group consisting of the general formulas (III-1) to (III-4) may be included as the main chain skeleton of the curing agent, It may be included as part. Further, each repeating unit constituting the structure represented by any one of the general formulas (III-1) to (III-4) may be included randomly or regularly. It may be included in a block shape.
  • the hydroxyl group substitution position is not particularly limited as long as it is on the aromatic ring.
  • a plurality of Ar 31 to Ar 34 may all be the same atomic group or may contain two or more atomic groups.
  • Ar 31 to Ar 34 each independently represent either a group represented by the general formula (III-a) or a group represented by the general formula (III-b).
  • R 31 and R 34 are each independently a hydrogen atom or a hydroxyl group, and preferably a hydroxyl group from the viewpoint of thermal conductivity. Further, the substitution positions of R 31 and R 34 are not particularly limited.
  • R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms in R 32 and R 33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, An octyl group etc. are mentioned.
  • substitution positions of R 32 and R 33 in the general formulas (III-a) and (III-b) are not particularly limited.
  • Ar 31 to Ar 34 are each independently a group derived from dihydroxybenzene (ie, from the viewpoint of achieving the effect of the present invention, particularly excellent thermal conductivity)
  • R 31 is a hydroxyl group and R 32 and R 33 are hydrogen atoms
  • R 34 is preferably at least one selected from the group consisting of a hydroxyl group.
  • group derived from dihydroxybenzene means a divalent group formed by removing two hydrogen atoms from the aromatic ring portion of dihydroxybenzene, and the position at which the hydrogen atom is removed is not particularly limited.
  • group derived from dihydroxynaphthalene has the same meaning.
  • Ar 31 to Ar 34 are preferably each independently a group derived from dihydroxybenzene, such as 1,2-dihydroxybenzene (catechol). More preferably, it is at least one selected from the group consisting of a group derived from and a group derived from 1,3-dihydroxybenzene (resorcinol). Furthermore, Ar 31 to Ar 34 preferably contain at least a group derived from resorcinol from the viewpoint of particularly enhancing the thermal conductivity. Further, from the viewpoint of particularly improving thermal conductivity, the structural unit represented by n31 to n34 preferably includes at least a partial structure derived from resorcinol.
  • the content of the partial structure derived from resorcinol is a structure represented by at least one of general formulas (III-1) to (III-4) It is preferably 55% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, based on the total mass of the compound having the above.
  • (m + n) is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less, from the viewpoint of fluidity.
  • the lower limit of (m + n) is not particularly limited.
  • the novolak resin having a structure represented by at least one selected from the group consisting of the general formulas (III-1) to (III-4) is particularly preferably a substituted or unsubstituted dihydroxybenzene in which Ar 31 to Ar 34 are substituted or unsubstituted.
  • a novolak resin or the like obtained by simply novolacizing these, the synthesis thereof is easy, and a novolak resin having a low softening point tends to be obtained. Therefore, there exists an advantage that manufacture and handling of such a novolak resin as a hardening
  • the novolak resin having the structure represented by any one of the above general formulas (III-1) to (III-4) is obtained as a fragment component of the above structure by field desorption ionization mass spectrometry (FD-MS). Can be specified.
  • the molecular weight of the novolak resin having a structure represented by any one of the general formulas (III-1) to (III-4) is not particularly limited.
  • the number average molecular weight (Mn) is preferably 2000 or less, more preferably 1500 or less, and further preferably 350 or more and 1500 or less.
  • the weight average molecular weight (Mw) is preferably 2000 or less, more preferably 1500 or less, and further preferably 400 or more and 1500 or less. These Mn and Mw are measured by a normal method using GPC.
  • the hydroxyl group equivalent of the novolak resin having a structure represented by any of the above general formulas (III-1) to (III-4) is not particularly limited. From the viewpoint of the crosslinking density involved in heat resistance, the hydroxyl group equivalent is preferably 50 to 150, more preferably 50 to 120, and even more preferably 55 to 120 on average.
  • the specific novolac resin may contain a monomer that is a phenol compound constituting the novolac resin.
  • a content ratio (henceforth "monomer content ratio") of the monomer which is a phenol compound which comprises specific novolak resin.
  • the monomer content is preferably 5% by mass to 80% by mass, more preferably 15% by mass to 60% by mass, and 20% by mass to 50% by mass. More preferably, it is mass%.
  • the monomer content is 80% by mass or less, the amount of monomers that do not contribute to crosslinking during the curing reaction is reduced and the number of crosslinked high molecular weight substances is increased, so that a higher-order higher-order structure is formed and heat conduction is increased. Improves. Moreover, since it is easy to flow at the time of shaping
  • the content of the curing agent in the epoxy resin composition is not particularly limited.
  • the ratio of the active hydrogen equivalent of the phenolic hydroxyl group (phenolic hydroxyl group equivalent) in the curing agent to the epoxy equivalent of the epoxy resin monomer represented by formula (I) (phenolic hydroxyl group equivalent / epoxy equivalent) is 0.5 to 2 is preferable, and 0.8 to 1.2 is more preferable.
  • the epoxy resin composition may further contain a curing accelerator as necessary.
  • a curing accelerator By further including a curing accelerator, it can be further sufficiently cured.
  • the type and content of the curing accelerator are not particularly limited, and an appropriate type and content can be selected from the viewpoint of reaction rate, reaction temperature, storage property, and the like.
  • Specific examples of the curing accelerator include imidazole compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, it is preferably at least one selected from the group consisting of an organic phosphine compound and a complex of an organic phosphine compound and an organic boron compound.
  • organic phosphine compound examples include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, and tris (dialkylphenyl).
  • Phosphine tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, Examples thereof include alkyl diaryl phosphine.
  • complexes of organic phosphine compounds and organic boron compounds include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetrabutylphosphonium tetraphenylborate, and tetraphenylphosphonium n-butyl.
  • examples thereof include triphenyl borate, butyl triphenyl phosphonium tetraphenyl borate, and methyl tributyl phosphonium tetraphenyl borate.
  • One curing accelerator may be used alone, or two or more curing accelerators may be used in combination.
  • a method for efficiently producing a semi-cured epoxy resin composition and a cured epoxy resin composition which will be described later, a method of mixing and using two kinds of curing accelerators having different reaction start temperatures and reaction rates between an epoxy resin monomer and a novolac resin Is mentioned.
  • the mixing ratio should be determined without any particular restrictions depending on the properties required for the semi-cured epoxy resin composition (for example, how much flexibility is required). Can do.
  • the content of the curing accelerator in the epoxy resin composition is not particularly limited.
  • the content of the curing accelerator is preferably 0.5% by mass to 1.5% by mass of the total mass of the thermosetting resin having a mesogenic group in the molecule and the curing agent. It is more preferably 5% by mass to 1% by mass, and further preferably 0.75% by mass to 1% by mass.
  • the epoxy resin composition includes an alumina filler containing ⁇ -alumina.
  • alumina By using alumina as a filler, it has excellent thermal conductivity, moldability, adhesiveness, mechanical strength, and electrical insulation.
  • thermal conductivity, mechanical strength, and electrical insulation are further improved. Excellent.
  • the alumina filler may further contain alumina other than ⁇ -alumina as necessary.
  • alumina other than ⁇ -alumina include ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and the like, but from the viewpoint of thermal conductivity, it is preferably composed only of ⁇ -alumina.
  • the shape of an alumina filler is round shape. The shape of the alumina filler can be confirmed by a scanning electron microscope (SEM).
  • ⁇ -alumina in the alumina filler can be confirmed by an X-ray diffraction spectrum. Specifically, according to the description in Japanese Patent No. 3759208, the presence of ⁇ -alumina can be confirmed using a peak peculiar to ⁇ -alumina as an index.
  • the content of ⁇ -alumina in the alumina filler is preferably 80% by volume or more, more preferably 90% by volume or more, and 100% by volume from the viewpoint of thermal conductivity and fluidity. More preferably.
  • an alumina filler having a large ⁇ -alumina content is used, the higher-order structure forming power resulting from the epoxy resin monomer represented by the general formula (I) is large, and a better thermal conductivity tends to be obtained. is there.
  • the content of ⁇ -alumina in the alumina filler can be confirmed by an X-ray diffraction spectrum.
  • the alumina filler content in the epoxy resin composition is not particularly limited.
  • the alumina filler content is preferably 60% by volume to 90% by volume in the total volume of the total solid content of the epoxy resin composition.
  • the thermal conductivity is more excellent.
  • a moldability and adhesiveness improve more that the content rate of an alumina filler is 90 volume% or less.
  • the content of the alumina filler is more preferably 65% by volume to 85% by volume and more preferably 70% by volume to 85% by volume in the total volume of the total solid content of the epoxy resin composition from the viewpoint of improving thermal conductivity. More preferably.
  • each variable is as follows.
  • Aw mass composition ratio of epoxy resin monomer (mass%)
  • Bw mass composition ratio (% by mass) of curing agent
  • Cw mass composition ratio (mass%) of curing accelerator (optional component)
  • Dw mass composition ratio of alumina filler (mass%)
  • Ew Mass composition ratio (% by mass) of other optional components (excluding organic solvents)
  • Ad Specific gravity of epoxy resin monomer
  • Bd Specific gravity of curing agent
  • Cd Specific gravity of curing accelerator (optional component)
  • Dd Specific gravity of alumina filler
  • Ed Specific gravity of other optional components (excluding organic solvent)
  • the alumina filler may have a single peak or a plurality of peaks when a particle size distribution curve is drawn with the particle diameter on the horizontal axis and the frequency on the vertical axis.
  • an average particle size (D50) which is a particle size corresponding to 50% weight cumulative from the small particle size side of the weight cumulative particle size distribution of the alumina filler.
  • D50 average particle size
  • the alumina filler having a plurality of peaks in the particle size distribution curve can be configured by combining two or more fillers having different average particle diameters (D50), for example.
  • the average particle diameter (D50) of the alumina filler is measured using a laser diffraction method, and corresponds to the particle diameter at which the weight accumulation becomes 50% when the weight accumulation particle size distribution curve is drawn from the small particle diameter side.
  • the particle size distribution measurement using the laser diffraction method can be performed using a laser diffraction scattering particle size distribution measuring device (for example, LS230 manufactured by Beckman Coulter, Inc.).
  • the alumina filler (A) having an average particle size (D50) of 10 ⁇ m or more and 100 ⁇ m or less, and an average particle size ( A mixed filler with an alumina filler (B) in which D50) is 1 ⁇ 2 or less of the filler (A) and is 0.1 ⁇ m or more and less than 10 ⁇ m can be mentioned.
  • the mixed filler is based on the total volume of the alumina filler (100 volume%), the alumina filler (A) is 60 volume% to 90 volume%, and the alumina filler (B) is 10 volume% to 40 volume% (however, the alumina filler
  • the total volume% of the fillers (A) and (B) is preferably 100% by volume).
  • a mixed filler with a certain alumina filler (C ') can be mentioned.
  • the mixed filler is based on the total volume of the alumina filler (100% by volume), 30% to 89% by volume of the alumina filler (A ′), 10% to 40% by volume of the alumina filler (B ′), and alumina.
  • the filler (C ′) is preferably 1 to 30% by volume (provided that the total volume% of the fillers (A ′), (B ′), and (C ′) is 100% by volume). is there.
  • the average particle diameter (D50) of the alumina fillers (A) and (A ′) is a cured epoxy in a target resin sheet or laminate when the epoxy resin composition is applied to a resin sheet or laminate described later.
  • the film thickness of the target prepreg and the fineness of the fiber substrate are selected as appropriate. It is preferable.
  • the average particle diameter of the fillers (A) and (A ′) is preferably as large as possible from the viewpoint of thermal conductivity.
  • the average particle diameter of the fillers (A) and (A ′) is preferably 10 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 80 ⁇ m from the viewpoint of filler filling property, thermal resistance, and thermal conductivity. It is more preferably from 1 to 50 ⁇ m, further preferably from 1 to 30 ⁇ m, and further preferably from 1 to 20 ⁇ m.
  • the epoxy resin composition may further contain an alumina filler having an average particle diameter (D50) of 1 nm or more and less than 100 nm (0.001 ⁇ m or more and less than 0.1 ⁇ m) as necessary.
  • D50 average particle diameter
  • the content of the alumina filler is not particularly limited.
  • the content of the alumina filler is preferably 0.01 vol% to 1 vol% in the total volume of the total solid content of the epoxy resin composition, preferably 0.01 vol% to 0.5 vol% More preferably it is contained.
  • the epoxy resin composition may further contain an inorganic filler other than the alumina filler as necessary.
  • inorganic fillers other than the alumina filler include boron nitride, aluminum nitride, silica, magnesium oxide, silicon nitride, and silicon carbide.
  • the content is preferably 50% by volume or less, more preferably 30% by volume or less with respect to the content of the alumina filler.
  • the epoxy resin composition preferably further contains an elastomer having at least a structural unit represented by the following general formula (IV) in the molecule.
  • an elastomer having at least a structural unit represented by the following general formula (IV) in the molecule By including the elastomer having the structural unit represented by the general formula (IV), the dispersibility of the alumina filler is further improved, and the flexibility of the B stage sheet described later is further improved.
  • effects such as improvement in density and reduction in insulation due to reduction of internal voids can be obtained.
  • R 41 , R 42 and R 43 each independently represent a linear or branched alkyl group or a hydrogen atom.
  • R 44 represents a linear or branched alkyl group.
  • n4 is an arbitrary integer indicating the number of structural units.
  • the elastomer is preferably a homopolymer or copolymer derived from at least one monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester.
  • an acrylic resin copolymer mainly containing a structural unit represented by the general formula (IV) as the elastomer it is preferable to use an acrylic resin copolymer mainly containing a structural unit represented by the general formula (IV) as the elastomer.
  • R 41 , R 42 or R 43 when any of R 41 , R 42 or R 43 is an alkyl group, the number of carbon atoms is preferably 1 to 12 from the viewpoint of imparting flexibility, and the low glass transition temperature (Tg ), The number of carbon atoms is more preferably 1-8.
  • R 41 and R 42 are each a hydrogen atom
  • R 43 is a hydrogen atom or a methyl group
  • R 41 , R 42 and R 43 are a hydrogen atom. .
  • R 44 is a linear or branched alkyl group.
  • the alkyl group for R 44 preferably has 2 to 16 carbon atoms from the viewpoint of imparting flexibility, and has 3 to 14 carbon atoms from the viewpoint of small inhibition of higher-order structure formation in the epoxy resin monomer. More preferably, it is more preferably 4 to 12 from the viewpoint of availability and ease of synthesis.
  • the elastomer preferably has a structural unit number of carbon atoms of the alkyl group represented by R 44 is represented by two or more different formula (IV).
  • the carbon number of the alkyl group in one structural unit may be 2 to 7 from the viewpoint of low Tg. Preferably, it is 3-6.
  • the carbon number of the alkyl group in the other structural unit is preferably 8 to 16 and more preferably 10 to 14 from the viewpoint of imparting flexibility.
  • n is an arbitrary integer indicating the number of structural units.
  • the number of structural units represented by n4 means the average value of the total number of structural units represented by the general formula (IV) contained in the elastomer molecule.
  • the elastomer having at least the structural unit represented by the general formula (IV) in the molecule preferably further has at least one of a carboxy group and a hydroxy group in the molecule, and has a structural unit having at least one of a carboxy group and a hydroxy group. It is more preferable that a structural unit having at least a carboxy group is included.
  • Examples of the monomer that can form a structural unit having a carboxy group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and the like. Among these, acrylic acid and methacrylic acid are preferable.
  • Examples of the monomer capable of forming a structural unit having a hydroxy group include (meth) acrylic acid esters containing a hydroxyalkyl group having 2 to 20 carbon atoms, and a hydroxyalkyl group having 2 to 6 carbon atoms can be exemplified. It is preferable that it is a (meth) acrylic ester containing. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.
  • a carboxy group or a hydroxyl group When a carboxy group or a hydroxyl group is present in the elastomer, they can undergo a crosslinking reaction with the epoxy resin monomer during the curing reaction, so that the crosslinking density is further improved, and as a result, the thermal conductivity can be further improved.
  • the carboxy group releases hydrogen ions, it is easy to open the epoxy group during the curing reaction, thereby providing an effect of acting as a catalyst.
  • the carboxy group acts with the hydroxyl group on the surface of the alumina filler, it brings about the effect of surface treatment on the alumina filler.
  • the effect of such a surface treatment is that the wettability between the alumina filler and the elastomer is improved, so that the viscosity of the epoxy resin composition (varnish) further containing a solvent tends to be lowered and the coating tends to be easy. Furthermore, the alumina filler is more highly dispersed by the improvement of wettability, which contributes to the improvement of thermal conductivity.
  • the content of the structural unit having at least one of carboxy group and hydroxy group contained in the elastomer is not particularly limited. From the viewpoint of filler dispersibility, the content of the structural unit having at least one of a carboxy group and a hydroxy group in the elastomer is preferably 10 mol% to 30 mol% based on the entire elastomer molecule (100 mol%). 14 mol% to 28 mol% is more preferable.
  • the elastomer having at least the structural unit represented by the general formula (IV) in the molecule preferably further contains at least one amino group in the molecule, and preferably contains at least one structural unit having an amino group. More preferred.
  • the amino group is preferably a secondary amino group or a tertiary amino group from the viewpoint of preventing moisture absorption. Further, from the viewpoint of improving thermal conductivity, an N-methylpiperidino group is particularly preferable. When an N-methylpiperidino group is present in the elastomer, the compatibility is remarkably improved by the interaction with a curing agent containing a novolac resin obtained by novolacizing a divalent phenol compound.
  • the acrylic monomer excellent in compatibility when added to an epoxy resin composition, the loss of heat conductivity becomes smaller.
  • the interaction between the N-methylpiperidino group and a curing agent containing a novolak resin in which a divalent phenol compound is novolaked exhibits a stress relaxation effect due to slippage between different types of molecules and contributes to further improvement in adhesive strength. It will be.
  • the content of the amino group contained in the elastomer is not particularly limited. From the viewpoint of compatibility, the content of the structural unit having an amino group in the elastomer is preferably 0.5 mol% to 5 mol%, more preferably 0.7 mol% to 3.5 mol%. preferable.
  • V an acrylic elastomer containing a structural unit represented by the following general formula (V)
  • the flexibility of the B stage sheet which is a semi-cured epoxy resin composition described later, is improved, and the internal voids in the resin sheet and prepreg described later are included. Effects such as density improvement and insulation improvement by reduction can be obtained more remarkably.
  • R 51 and R 52 each independently represent a linear or branched alkyl group having a different carbon number.
  • R 53 to R 56 each independently represents a hydrogen atom or a methyl group.
  • a + b + c + d 90 mol% or more, preferably 95 mol% or more, and more preferably 99 mol% or more.
  • the structural unit (hereinafter also referred to as “structural unit a”) present in the proportion of a can impart flexibility to the resin sheet and can also conduct heat. It is possible to achieve both sex and flexibility. Further, the structural unit present in the ratio of b (hereinafter also referred to as “structural unit b”) makes the flexibility of the resin sheet more preferable in the combination with the structural unit a shown above.
  • the carbon number of the alkyl group represented by R 51 and R 52 in the structural units a and b that imparts a soft structure (flexibility) is not particularly limited.
  • the carbon number of the alkyl group of R 51 and R 52 is preferably in the range of 2 to 16, more preferably in the range of 3 to 14, and still more preferably in the range of 4 to 12.
  • the alkyl groups represented by R 51 and R 52 have different carbon numbers.
  • the difference in carbon number between R 51 and R 52 is not particularly limited, but the difference in carbon number is preferably 4 to 10 and more preferably 6 to 8 from the viewpoint of the balance between flexibility and flexibility.
  • R 51 has preferably 2 to 6 carbon atoms
  • R 52 preferably has 8 to 16 carbon atoms
  • R 51 has 3 to 5 carbon atoms. More preferably, R 52 has 10 to 14 carbon atoms.
  • the range of mol% of the structural units a and b is not particularly limited. Further, the ratio between the structural units a and b may be arbitrary. It is preferable to use an acrylic elastomer that includes a combination of structural units a and b, rather than any of structural units a and b.
  • the combination of structural units a and b may increase the number of side chains and increase the flexibility of the acrylic elastomer, and may increase Tg. However, Tg can be controlled within a suitable range by appropriately adjusting the proportion of mol% of the structural units a and b in the acrylic elastomer.
  • the content of the structural unit a is preferably 50 mol% to 85 mol%, more preferably 60 mol% to 80 mol%.
  • the content of the structural unit b is preferably 2 mol% to 20 mol%, more preferably 5 mol% to 15 mol%.
  • the content ratio of the structural unit a to the structural unit b is preferably 4 to 10, and more preferably 6 to 8.
  • the presence of a carboxy group in the acrylic elastomer derived from the structural unit present in the proportion of c improves thermal conductivity and The effect of improving the wettability between the filler and the resin is obtained.
  • structural unit d due to the presence of N-methylpiperidino group in the acrylic elastomer derived from the structural unit present in the proportion of d (hereinafter also referred to as “structural unit d”), the compatibility and adhesion are improved. An effect is obtained.
  • the N-methylpiperidino group can accept hydrogen ions from a carboxy group and then allows interaction with a novolak resin, for example, included as a curing agent.
  • a novolak resin for example, included as a curing agent.
  • the compatibility with the acrylic elastomer in the epoxy resin composition is improved by the interaction with the novolac resin.
  • the intramolecular interaction between the carboxy group and the N-methylpiperidino group contributes to the stress relaxation due to the low elasticity. This can be considered, for example, because the entire molecule of the acrylic elastomer has a curved structure instead of a linear structure.
  • the proportion of the structural units c and d is preferably in the range of 10 mol% to 28 mol%, more preferably It is in the range of 14 mol% to 28 mol%, more preferably in the range of 20 mol% to 28 mol%, and d is preferably in the range of 0.5 mol% to 5 mol%, more preferably from 0.7 mol% to It is in the range of 3.5 mol%, more preferably in the range of 0.7 mol% to 1.4 mol%.
  • the content ratio of the structural unit c to the structural unit d is preferably 0.01 to 0.5, more preferably 0.03 to 0.3, and still more preferably 0.035 to 0.25.
  • R 53 to R 56 are each independently a hydrogen atom or a methyl group, but it is preferable that at least one of R 53 and R 54 is a hydrogen atom and the other is a methyl group, and R 53 is a hydrogen atom and R 54 is More preferred is a methyl group. Also preferably the other is a methyl group at least one hydrogen atom of the pair of R 55 and R 56, and more preferably R 56 R 55 is a hydrogen atom is a methyl group.
  • the acrylic elastomer having the structure represented by the general formula (V) may further contain structural units other than the structural units a to d.
  • the structural unit other than the structural units a to d is not particularly limited. Examples of the structural unit other than the structural units a to d include a structural unit derived from a (meth) acrylic acid ester containing a hydroxyalkyl group and a structural unit derived from a (meth) acrylic acid ester containing a tertiary amino group. Can do.
  • the content of structural units other than the structural units a to d in the acrylic elastomer is 10 mol% or less, preferably 5 mol% or less, and more preferably 1 mol% or less.
  • the weight average molecular weight of the acrylic elastomer is not particularly limited. Among these, from the viewpoint of thermal conductivity and flexibility, it is preferably 10,000 to 100,000, more preferably 10,000 to 50,000, and 10,000 to 30,000. Is more preferable. Furthermore, when the weight average molecular weight of the acrylic elastomer is within the above range, the dispersibility of the inorganic filler is further improved, and the viscosity of the epoxy resin composition tends to be further decreased. The weight average molecular weight of the acrylic elastomer is measured by a normal method using GPC.
  • the content of the acrylic elastomer is 0.1 to 99 parts by mass when the total mass of the epoxy resin components (epoxy resin monomer and curing agent) is 100 parts by mass.
  • the range is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass.
  • the content of the acrylic elastomer is 0.1 parts by mass or more, a decrease in thermal conductivity is further suppressed, and the adhesive force with the adherend tends to be further improved.
  • the amount is 99 parts by mass or less of the acrylic elastomer, a decrease in the adhesive force with the adherend is further suppressed, and the thermal conductivity tends to be further improved. Therefore, it becomes easy to express various characteristics in a well-balanced manner by adjusting the content of the acrylic elastomer to the above range.
  • the epoxy resin composition preferably further includes at least one silane coupling agent.
  • silane coupling agent As an effect of adding a silane coupling agent, it plays the role of forming a covalent bond between the surface of the alumina filler and the thermosetting resin surrounding it (equivalent to the binder agent), and the effect of transferring heat more efficiently
  • an effect of improving insulation reliability can be obtained by preventing moisture from entering.
  • the type of the silane coupling agent is not particularly limited and can be appropriately selected from commercially available ones.
  • a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, a ureido group and a hydroxyl group at the terminal.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane.
  • Silane coupling agents having an epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- Silane coupling agents having an amino group such as (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercapto G Silane coupling agent having a ureido group such as 3-ureidopropyltriethoxysilane; silane coupling agent having a mercapto group such as silane, and the like. Further, silane coupling agent oligomers (manufactured by Hitachi Chemical Coated Sand Co., Ltd.) represented by SC-6000KS2
  • the epoxy resin composition may further contain at least one organic solvent.
  • organic solvent By including an organic solvent, it can be easily adapted to various molding processes.
  • the organic solvent can be appropriately selected from commonly used organic solvents. Specific examples include alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents, sulfoxide solvents, and the like.
  • organic solvents include ketone solvents such as methyl isobutyl ketone, cyclohexanone, and methyl ethyl ketone; amide solvents such as dimethylacetamide, dimethylformamide, and N-methyl-2-pyrrolidone; ester solvents such as ⁇ -butyrolactone; dimethyl sulfoxide, sulfolane And the like can be used. These may be used alone or as a mixed solvent using two or more kinds in combination.
  • the epoxy resin composition can contain other components as required in addition to the above components.
  • examples of other components include a dispersant.
  • examples of the dispersant include Ajinomoto Finetech Co., Ltd. Ajisper series, Enomoto Kasei Co., Ltd. HIPLAAD series, Kao Corporation homogenol series, and the like. These may be used alone or in combination of two or more.
  • the semi-cured epoxy resin composition of the present invention is derived from the epoxy resin composition, and is obtained by semi-curing the epoxy resin composition. For example, when the semi-cured epoxy resin composition is molded into a sheet shape, the handleability is improved as compared with a resin sheet made of an epoxy resin composition that is not semi-cured.
  • the semi-cured epoxy resin composition means that the viscosity of the semi-cured epoxy resin composition is 10 4 Pa ⁇ s to 10 5 Pa ⁇ s at room temperature (25 to 30 ° C.). It has a feature that it decreases to 10 2 Pa ⁇ s to 10 3 Pa ⁇ s at a temperature of 0 ° C. Moreover, the cured epoxy resin composition after curing described later does not melt by heating.
  • the viscosity is measured by dynamic viscoelasticity measurement (DMA) (for example, ARES-2KSTD manufactured by TA Instruments). The measurement conditions are a frequency of 1 Hz, a load of 40 g, a temperature increase rate of 3 ° C./min, and a shear test.
  • DMA dynamic viscoelasticity measurement
  • Examples of the semi-curing treatment include a method of heating the epoxy resin composition at a temperature of 100 ° C. to 200 ° C. for 1 minute to 30 minutes.
  • the cured epoxy resin composition of the present invention is derived from the epoxy resin composition, and is obtained by curing the epoxy resin composition.
  • the cured epoxy resin composition is excellent in thermal conductivity.
  • the epoxy resin monomer represented by the general formula (I) having a mesogenic group in the molecular structure contained in the epoxy resin composition is an ⁇ -alumina filler. It can be considered that a higher-order structure is formed around the center.
  • the said cured epoxy resin composition is excellent in heat resistance.
  • the cured epoxy resin composition can be produced by curing the uncured epoxy resin composition or the semi-cured epoxy resin composition.
  • the method of the said hardening process can be suitably selected according to the structure of an epoxy resin composition, the objective of a cured epoxy resin composition, etc., it is preferable that they are a heating and a pressurization process.
  • an uncured epoxy resin composition or the semi-cured epoxy resin composition is heated at 100 ° C. to 250 ° C. for 1 hour to 10 hours, preferably at 130 ° C. to 230 ° C. for 1 hour to 8 hours.
  • a resin composition is obtained.
  • the resin sheet of the present invention is formed by molding the epoxy resin composition into a sheet shape.
  • the said resin sheet can be manufactured by providing the said epoxy resin composition on a release film, for example, and removing the solvent contained as needed.
  • the resin sheet is excellent in thermal conductivity and heat resistance by being formed from the epoxy resin composition.
  • the density of the resin sheet is not particularly limited, and can be, for example, 3.0 g / cm 2 to 3.5 g / cm 2 . In consideration of the compatibility between the flexibility and the thermal conductivity of the resin sheet, 3.1 g / cm 2 to 3.4 g / cm 2 is preferable, and 3.1 g / cm 2 to 3.3 g / cm 2 is more preferable.
  • the density of the resin sheet can be adjusted, for example, by appropriately selecting the content of the alumina filler in the epoxy resin composition.
  • the thickness of the resin sheet is not particularly limited and can be appropriately selected depending on the purpose.
  • the thickness of the resin sheet can be 50 ⁇ m to 500 ⁇ m, and is preferably 80 ⁇ m to 300 ⁇ m from the viewpoint of thermal conductivity, electrical insulation, and flexibility.
  • the resin sheet is a varnish-like epoxy resin composition (hereinafter referred to as “resin varnish”) prepared by adding an organic solvent such as methyl ethyl ketone or cyclohexanone to the epoxy resin composition on a release film such as a PET film. Can be produced by removing at least a part of the organic solvent from the coating layer and drying.
  • resin varnish a varnish-like epoxy resin composition
  • the resin varnish can be performed by a known method. Specific examples include methods such as comma coating, die coating, lip coating, and gravure coating.
  • the coating method for forming the epoxy resin composition layer to a predetermined thickness include a comma coating method in which an object to be coated is passed between gaps, and a die coating method in which a resin varnish with a flow rate adjusted from a nozzle is applied. .
  • the thickness of the coating layer (resin composition layer) before drying is 50 ⁇ m to 500 ⁇ m, it is preferable to use a comma coating method.
  • the drying method is not particularly limited as long as at least a part of the organic solvent contained in the resin varnish can be removed, and can be appropriately selected from commonly used drying methods according to the organic solvent contained in the resin varnish. In general, a heat treatment method at about 80 ° C. to 150 ° C. can be mentioned.
  • the epoxy resin composition layer of the resin sheet hardly undergoes a curing reaction, it has flexibility, but the sheet has poor flexibility, and in the state where the PET film as a support is removed, the sheet is self-supporting. It may be difficult to handle.
  • the resin sheet is preferably a semi-cured epoxy resin composition obtained by semi-curing an epoxy resin composition constituting the resin sheet. That is, the resin sheet is preferably a B stage sheet that is further heat-treated until it is in a semi-cured state (B stage state). Since the resin sheet is composed of a semi-cured epoxy resin composition obtained by semi-curing the epoxy resin composition, it has excellent thermal conductivity and heat resistance, and is flexible and usable as a B-stage sheet. Excellent.
  • the B stage sheet has a viscosity of 10 4 Pa ⁇ s to 10 5 Pa ⁇ s at room temperature (25 to 30 ° C.), whereas it has a viscosity of 10 2 Pa ⁇ s to 10 3 Pa at 100 ° C. -It has the characteristic which falls to s.
  • the cured epoxy resin composition after curing described later is not melted by heating. The viscosity is measured by DMA (frequency 1 Hz, load 40 g: temperature rising rate 3 ° C./min).
  • the conditions for heat-treating the resin sheet are not particularly limited as long as the epoxy resin composition layer can be in a B-stage state, and can be appropriately selected according to the configuration of the epoxy resin composition.
  • a heat treatment method selected from hot vacuum press, hot roll laminating and the like is preferable for the purpose of eliminating voids in the resin layer generated during coating. Thereby, a flat B stage sheet
  • the epoxy resin composition is heated and pressurized under reduced pressure (eg, 1 kPa) at a temperature of 100 ° C. to 200 ° C. for 1 minute to 3 minutes with a press pressure of 1 MPa to 5 MPa. It can be semi-cured to the B stage state.
  • reduced pressure eg, 1 kPa
  • the thickness of the B stage sheet can be appropriately selected according to the purpose, and can be, for example, 50 ⁇ m to 500 ⁇ m, and is 80 ⁇ m to 300 ⁇ m from the viewpoint of thermal conductivity, electrical insulation, and flexibility. It is preferable.
  • the solvent remaining rate in the B-stage sheet is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of suppressing bubble formation due to outgas generation during curing. More preferably, it is 5 mass% or less.
  • the solvent residual rate is determined from the change in mass before and after drying when a B-stage sheet is cut into a 40 mm square and dried in a thermostat preheated to 190 ° C. for 2 hours.
  • the B stage sheet has excellent fluidity.
  • the flow amount in the B stage sheet is preferably 130% to 210%, and more preferably 150% to 200%. This flow amount is an indicator of melt fluidity during thermocompression bonding. When the flow amount is 130% or more, sufficient embeddability can be obtained, and when it is 210% or less, generation of burrs due to excessive flow can be suppressed.
  • the amount of flow is as follows. When a sample obtained by punching a 200 mm square B stage sheet into a 10 mm square was pressed for 1 minute under atmospheric pressure conditions at a temperature of 160 ° C. and a press pressure of 1.6 MPa, Calculated as the area change rate.
  • the area change rate is obtained from the change rate of the area (number of pixels) after taking the external projection image of the sample with a scanner of 300 DPI or more, binarizing with an image analysis software (Adobe Photoshop).
  • the resin sheet may be a cured epoxy resin composition obtained by curing the epoxy resin composition.
  • a resin sheet made of a cured epoxy resin composition can be produced by curing an uncured resin sheet or B-stage sheet.
  • the method of the said hardening process can be suitably selected according to the structure of an epoxy resin composition, the objective of a cured epoxy resin composition, etc., it is preferable that they are a heating and a pressurization process.
  • a resin comprising a cured epoxy resin composition by heating an uncured resin sheet or B stage sheet at 100 ° C. to 250 ° C. for 1 hour to 10 hours, preferably 130 ° C. to 230 ° C. for 1 hour to 8 hours.
  • a sheet is obtained.
  • the heating is preferably performed while applying a pressure of 1 MPa to 5 MPa.
  • the following method is mentioned as an example of the method of manufacturing the resin sheet which consists of a cured epoxy resin composition which has high heat conductivity and high heat resistance.
  • the B stage sheet is sandwiched between two copper foils (thickness: 80 ⁇ m to 120 ⁇ m) each having a rough surface, and the temperature is 130 ° C. to 230 ° C. for 3 minutes to 10 minutes. Heating and pressing are performed with a press pressure of 1 MPa to 5 MPa to bond the B stage sheet and the copper foil.
  • the epoxy resin composition is cured by heating at 130 to 230 ° C. for 1 to 8 hours to obtain a resin sheet with copper foil.
  • There is a method of obtaining a resin sheet made of a cured epoxy resin composition by removing a copper foil portion of the obtained resin sheet with a copper foil by etching treatment.
  • the prepreg of the present invention includes a fiber base material and the epoxy resin composition impregnated in the fiber base material. With such a configuration, a prepreg excellent in thermal conductivity and heat resistance is obtained. Moreover, since the thixotropy improves the epoxy resin composition containing an alumina filler, it can suppress sedimentation of the alumina filler in the below-mentioned coating process or impregnation process. Therefore, the occurrence of the density distribution of the alumina filler in the thickness direction of the prepreg can be suppressed, and as a result, a prepreg excellent in thermal conductivity and heat resistance can be obtained.
  • the fiber base material constituting the prepreg is not particularly limited as long as it is usually used when producing a metal foil-clad laminate or a multilayer wiring board, and is appropriately selected from fiber base materials such as woven fabrics and nonwoven fabrics that are usually used. Selected.
  • the opening of the fiber base material is not particularly limited. From the viewpoint of thermal conductivity and electrical insulation, the mesh opening is preferably 5 times or more the average particle diameter (D50) of the alumina filler. Further, when the particle size distribution curve of the alumina filler has a plurality of peaks, it is more preferable that the opening is 5 times or more the particle diameter corresponding to the peak having the largest particle diameter.
  • the material of the fiber base material is not particularly limited. Specifically, inorganic fibers such as glass, alumina, boron, silica alumina glass, silica glass, tyranno, silicon carbide, silicon nitride, zirconia, carbon, aramid, polyetheretherketone, polyetherimide, polyether Examples thereof include organic fibers such as sulfone and cellulose, and mixed papers thereof.
  • a glass fiber woven fabric is preferably used as the fiber base material.
  • a wiring board is configured using prepreg, a wiring board that is flexible and can be arbitrarily bent can be obtained. Furthermore, it becomes possible to reduce the dimensional change of the wiring board accompanying the temperature change, moisture absorption, etc. in the manufacturing process.
  • the thickness of the fiber base material is not particularly limited. From the viewpoint of imparting better flexibility, the thickness is more preferably 30 ⁇ m or less, and from the viewpoint of impregnation, it is preferably 15 ⁇ m or less. Although the minimum of the thickness of a fiber base material is not restrict
  • the impregnation amount (content ratio) of the epoxy resin composition in the prepreg is preferably 50% by mass to 99.9% by mass in the total mass of the fiber base material and the epoxy resin composition.
  • the prepreg is produced by impregnating a fiber base material with the epoxy resin composition prepared in a varnish form in the same manner as described above, and removing at least a part of the organic solvent by a heat treatment at 80 ° C. to 150 ° C. Can do.
  • the method for impregnating the fiber base material with the epoxy resin composition there is no particular limitation on the method for impregnating the fiber base material with the epoxy resin composition.
  • coating with a coating machine can be mentioned.
  • a vertical coating method in which a fiber base material is pulled up by passing through an epoxy resin composition a horizontal coating method in which an epoxy resin composition is coated on a support film and then impregnated by pressing the fiber base material, etc. be able to. From the viewpoint of suppressing the uneven distribution of the alumina filler in the fiber base material, the horizontal coating method is preferable.
  • the prepreg in the present invention may be used after the surface has been smoothed in advance by hot pressing with a press, a roll laminator or the like before laminating or sticking.
  • the method of the hot press treatment is the same as the method mentioned in the method for producing the B stage sheet.
  • the processing conditions such as the heating temperature, the degree of pressure reduction, and the pressing pressure in the hot pressurizing process of the prepreg are the same as the conditions mentioned in the heating and pressurizing process of the B stage sheet.
  • the solvent residual ratio in the prepreg is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.5% by mass or less.
  • the solvent residual rate is determined from the mass change before and after drying when the prepreg is cut into 40 mm square and dried in a thermostat preheated to 190 ° C. for 2 hours.
  • the laminate in the present invention has an adherend and a semi-cured epoxy resin composition layer or a cured epoxy resin composition layer disposed on the adherend.
  • the semi-cured epoxy resin composition layer and the cured epoxy resin composition layer are derived from at least one selected from the group consisting of an epoxy resin composition layer composed of the epoxy resin composition, the resin sheet, and the prepreg. It is at least one selected from the group consisting of a semi-cured epoxy resin composition layer and a cured epoxy resin composition layer.
  • adherend examples include metal foil and metal plate.
  • the adherend may be attached to only one side of the semi-cured epoxy resin composition layer or the cured epoxy resin composition layer, or may be attached to both sides.
  • the metal foil is not particularly limited and can be appropriately selected from commonly used metal foils. Specifically, gold foil, copper foil, aluminum foil, etc. can be mentioned, and copper foil is generally used.
  • the thickness of the metal foil is not particularly limited as long as it is 1 ⁇ m to 200 ⁇ m, and a suitable thickness can be selected according to the electric power used.
  • nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy or the like is used as an intermediate layer, and a copper layer of 0.5 ⁇ m to 15 ⁇ m and a layer of 10 ⁇ m to A three-layer composite foil provided with a 150 ⁇ m copper layer, or a two-layer composite foil in which aluminum and copper foil are combined can also be used.
  • the metal plate is preferably made of a metal material having high thermal conductivity and a large heat capacity. Specific examples include copper, aluminum, iron, alloys used for lead frames, and the like.
  • the thickness of the metal plate can be appropriately selected according to the application.
  • the material of the metal plate can be selected according to the purpose, such as selecting aluminum when priority is given to weight reduction or workability, and selecting copper when priority is given to heat dissipation.
  • a semi-cured epoxy resin composition layer or a cured epoxy resin composition layer in a form having one layer derived from any one of the epoxy resin composition layer, the resin sheet, or the prepreg.
  • two or more epoxy resin composition layers, two or more resin sheets, and two prepregs are used. Any form having at least one sheet may be used. Furthermore, you may have combining any 2 or more of the said epoxy resin composition layer, the said resin sheet, and the said prepreg.
  • the laminated board in the present invention forms the epoxy resin composition layer by applying the epoxy resin composition on an adherend, and heats and pressurizes it to semi-cur the epoxy resin composition layer. Or it is obtained by making it harden
  • the curing method for semi-curing or curing the epoxy resin composition layer, the resin sheet, and the prepreg is not particularly limited.
  • heat treatment and pressure treatment are preferable.
  • the heating temperature in the heating and pressure treatment is not particularly limited. Usually, it is in the range of 100 ° C to 250 ° C, preferably in the range of 130 ° C to 230 ° C.
  • the pressurization conditions in a heating and pressurizing process are not specifically limited. Usually, it is in the range of 1 MPa to 10 MPa, preferably in the range of 1 MPa to 5 MPa.
  • a vacuum press is used suitably for a heating and pressurizing process.
  • the thickness of the laminate is preferably 500 ⁇ m or less, and more preferably 100 ⁇ m to 300 ⁇ m.
  • the thickness is 500 ⁇ m or less, the flexibility is excellent and the occurrence of cracks during bending is suppressed, and when the thickness is 300 ⁇ m or less, this tendency is more apparent. Further, when the thickness is 100 ⁇ m or more, the workability is excellent.
  • the said resin cured body with metal foil is comprised using two metal foils as the adherend in the said laminated board. Specifically, one metal foil, the cured epoxy resin composition layer, and the other metal foil are laminated in this order. Details of the metal foil and the cured epoxy resin composition layer constituting the cured resin body with metal foil are as described above.
  • the said metal substrate is comprised using a metal foil and a metal plate as an adherend in the said laminated board.
  • the metal substrate is configured by laminating the metal foil, the cured epoxy resin composition layer, and the metal plate in this order. The details of the metal foil and the cured epoxy resin composition layer constituting the metal substrate are as described above.
  • the metal plate is not particularly limited, and can be appropriately selected from commonly used metal plates. Specifically, an aluminum plate, an iron plate, etc. can be mentioned.
  • the thickness of the metal plate is not particularly limited. From the viewpoint of workability, the thickness is preferably 0.5 mm or more and 5 mm or less.
  • the metal plate is preferably cut to a size to be used after being manufactured in a size larger than necessary and mounting an electronic component. Therefore, it is desirable that the metal plate used for the metal substrate is excellent in cutting workability.
  • aluminum or an alloy mainly composed of aluminum can be selected as the material.
  • Many types of aluminum or alloys containing aluminum as a main component are available depending on the chemical composition and heat treatment conditions. Among them, it is preferable to select a type having high workability such as easy cutting and excellent strength.
  • the wiring board of the present invention is formed by laminating a metal plate, a cured epoxy resin composition layer, and a wiring layer in this order.
  • the cured epoxy resin composition layer is a cured epoxy resin composition layer derived from at least one selected from an epoxy resin composition layer composed of the epoxy resin composition, the resin sheet, and the prepreg.
  • the wiring board can be produced by subjecting at least one metal foil in the above-described cured resin body with a metal foil or metal foil on a metal substrate to circuit processing.
  • An ordinary photolithography method can be applied to the circuit processing of the metal foil.
  • Preferred embodiments of the wiring board are, for example, the same as the wiring board described in paragraph No. 0064 of JP2009-214525A and the wiring boards described in paragraph Nos. 0056 to 0059 of JP2009-275086A. Can be mentioned.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a power semiconductor device.
  • the cured resin sheet 2 is disposed between the metal plate 6 and the heat dissipation base substrate 4 in the semiconductor module in which the metal plate 6, the solder layer 10, and the semiconductor chip 8 are laminated in this order, and the semiconductor module is sealed. Sealed with a stopper 14.
  • FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the power semiconductor device. In FIG.
  • the resin sheet cured body 2 is disposed between the metal plate 6 and the heat dissipation base substrate 4 in the semiconductor module in which the metal plate 6, the solder layer 10, and the semiconductor chip 8 are laminated in this order.
  • the base substrate 4 is molded with a mold resin 12.
  • the cured body of the resin sheet which is a sheet-like molded body of the epoxy resin composition of the present invention, can be used as a heat radiation adhesive layer between the semiconductor module and the heat radiation base substrate as shown in FIG. It is.
  • the whole is molded as shown in FIG. 2, it can be used as a heat dissipation material between the heat dissipation base substrate and the metal plate.
  • Curing agent 1 [catechol novolac resin, manufactured by Hitachi Chemical Co., Ltd., containing 50% cyclohexanone]
  • ⁇ Method for synthesizing curing agent 1 Catechol 220g, 37% formaldehyde 81.1g, oxalic acid 2.5g, and water 100g were placed in a 2L separable flask equipped with a stirrer, cooler, and thermometer, and heated to about 100 ° C while heating in an oil bath. The temperature rose. The mixture was refluxed at around 104 ° C., and the reaction was continued at the reflux temperature for 3 hours. Thereafter, the temperature in the flask was raised to 150 ° C. while distilling off water. The reaction was continued for 12 hours while maintaining 150 ° C.
  • Curing agent 2 [catechol resorcinol novolak (preparation ratio: 30/70) resin, manufactured by Hitachi Chemical Co., Ltd., containing 50% cyclohexanone]
  • ⁇ Method for synthesizing curing agent 2 462 g of resorcinol, 198 g of catechol, 316.2 g of 37% formaldehyde, 15 g of oxalic acid, and 300 g of water are placed in a 3 L separable flask equipped with a stirrer, a cooler, and a thermometer. The temperature rose. The mixture was refluxed at around 104 ° C., and the reaction was continued at the reflux temperature for 4 hours. Thereafter, the temperature in the flask was raised to 170 ° C. while distilling off water. The reaction was continued for 8 hours while maintaining 170 ° C.
  • Curing agent 3 [catechol resorcinol novolak (preparation ratio: 5/95) resin, manufactured by Hitachi Chemical Co., Ltd., containing 50% cyclohexanone]
  • the physical property values were measured as follows.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using a high performance liquid chromatography L6000 manufactured by Hitachi, Ltd. and a data analyzer C-R4A manufactured by Shimadzu Corporation.
  • G2000HXL and G3000HXL manufactured by Tosoh Corporation were used as analytical GPC columns, the sample concentration was 0.2% by mass, tetrahydrofuran was used as the mobile phase, and measurement was performed at a flow rate of 1.0 ml / min.
  • a calibration curve was prepared using a polystyrene standard sample, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured in terms of polystyrene using the standard curve.
  • the hydroxyl equivalent was measured by acetyl chloride-potassium hydroxide titration method.
  • the determination of the titration end point was performed by potentiometric titration rather than coloration with an indicator because the solution color was dark.
  • the hydroxyl group of the phenol resin to be measured is acetylated with acetyl chloride in a pyridine solution, the excess reagent is decomposed with water, and the acetic acid produced is titrated with a potassium hydroxide / methanol solution to measure the hydroxyl group equivalent. did.
  • the physical property values of the curing agents 1 to 3 are shown below.
  • Allumina filler AA-18 [ ⁇ -alumina, manufactured by Sumitomo Chemical Co., Ltd., average particle size (D50): 18 ⁇ m] AA-3 [ ⁇ -alumina, manufactured by Sumitomo Chemical Co., Ltd., average particle size (D50): 3 ⁇ m] AA-04 [ ⁇ -alumina, manufactured by Sumitomo Chemical Co., Ltd., average particle size (D50): 0.4 ⁇ m]
  • TPP Triphenylphosphine
  • KBM-573 3-phenylaminopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd.]
  • Example 1 Preparation of epoxy resin composition> 15.62 parts by mass of resin monomer A, 16.51 parts by mass of curing agent 1, 225.4 parts by mass of alumina filler (AA-18: 148.76 parts by mass (66% by volume), AA-3: 54 10 parts by mass (24% by volume), AA-04: 22.54 parts by mass (10% by volume)), 0.19 parts by mass of TPP, 0.24 parts by mass of KBM-573, and a total of 51 organic solvents. .44 parts by mass (MEK: 44.77 parts by mass, CHN: 6.67 parts by mass) were mixed to obtain an epoxy resin varnish as an epoxy resin composition containing an organic solvent.
  • MEK 44.77 parts by mass
  • CHN 6.67 parts by mass
  • the ratio of the alumina filler to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler, where the density of the mixture of the resin monomer A and the curing agent 1 is 1.20 g / cm 3 and the density of the alumina filler is 3.97 g / cm 3 was calculated to be 74% by volume.
  • ⁇ Preparation of semi-cured epoxy resin composition The epoxy resin varnish was coated on a PET film using an applicator so that the thickness after drying was 200 ⁇ m, and then dried at room temperature (20 ° C. to 30 ° C.) for 15 minutes and further at 130 ° C. for 5 minutes. Then, hot pressurization (press temperature: 130 ° C., vacuum degree: 1 kPa, press pressure: 1 MPa, pressurization time: 1 minute) is performed in a vacuum press, and a sheet-like semi-cured epoxy resin composition having a thickness of 190 ⁇ m I got a thing.
  • ⁇ Preparation of cured epoxy resin composition with copper foil> After peeling off the PET film from the sheet-like semi-cured epoxy resin composition obtained above, the two copper foils are used so that the mat surfaces of the two copper foils face the semi-cured epoxy resin composition, respectively.
  • the semi-cured epoxy resin composition was sandwiched and vacuum thermocompression-bonded with a vacuum press (temperature: 150 ° C. to 180 ° C., vacuum degree: 1 kPa, press pressure: 4 MPa, pressurization time: 5 minutes). Then, it heated at 140 degreeC for 2 hours, 165 degreeC for 2 hours, and also at 190 degreeC for 2 hours under atmospheric pressure conditions, and obtained the cured epoxy resin composition with copper foil.
  • the copper foil of the cured epoxy resin composition with copper foil obtained above was removed by etching to obtain a sheet-shaped cured epoxy resin composition.
  • the obtained cured epoxy resin composition was cut into a 10 mm square and blackened with a graphite spray, and then the thermal diffusivity was evaluated by a xenon flash method (LFA447 nanoflash manufactured by NETZSCH).
  • the thermal conductivity of the cured epoxy resin composition was determined from the product of this value, the density measured by the Archimedes method, and the specific heat measured by DSC (DSC Pyris 1 manufactured by Perkin Elmer). The obtained thermal conductivity results are shown in Table 1.
  • Tg glass transition temperature
  • Example 2 15.82 parts by mass of resin monomer A, 16.12 parts by mass of curing agent 2, 225.4 parts by mass of alumina filler (AA-18: 148.76 parts by mass (66% by volume), AA-3: 54 10 parts by mass (24% by volume), AA-04: 22.54 parts by mass (10% by volume)), 0.19 parts by mass of TPP, 0.24 parts by mass of KBM-573, and a total of 51 organic solvents. .63 parts by mass (MEK: 44.77 parts by mass, CHN: 6.86 parts by mass) were mixed to obtain an epoxy resin varnish as an epoxy resin composition containing an organic solvent.
  • MEK 44.77 parts by mass
  • CHN 6.86 parts by mass
  • the density of the mixture of the resin monomer A and the curing agent 2 is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3
  • the alumina filler with respect to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler The ratio was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • Example 3 18.48 parts by mass of resin monomer A, 10.81 parts by mass of curing agent 3, and 225.4 parts by mass of alumina filler (AA-18: 148.76 parts by mass (66% by volume), AA-3: 54 10 parts by mass (24% by volume), AA-04: 22.54 parts by mass (10% by volume)), 0.19 parts by mass of TPP, 0.24 parts by mass of KBM-573, and a total of 54 organic solvents. .29 parts by mass (MEK: 44.77 parts by mass, CHN: 9.52 parts by mass) were mixed to obtain an epoxy resin varnish as an epoxy resin composition containing an organic solvent.
  • the density of the mixture of the resin monomer A and the curing agent 3 is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3
  • the alumina filler with respect to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler The ratio was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • Example 4 18.61 parts by mass of resin monomer B, 10.54 parts by mass of curing agent 3, and 225.4 parts by mass of alumina filler (AA-18: 148.76 parts by mass (66% by volume), AA-3: 54 10 parts by mass (24% by volume), AA-04: 22.54 parts by mass (10% by volume)), 0.19 parts by mass of TPP, 0.24 parts by mass of KBM-573, and a total of 54 organic solvents. .42 parts by mass (MEK: 44.77 parts by mass, CHN: 9.65 parts by mass) were mixed to obtain an epoxy resin varnish as an epoxy resin composition containing an organic solvent.
  • MEK 44.77 parts by mass
  • CHN 9.65 parts by mass
  • the density of the mixture of the resin monomer B and the curing agent 3 is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3.
  • the alumina filler with respect to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler The ratio was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • Example 5 18.49 parts by mass of resin monomer A, 10.78 parts by mass of curing agent 3, and 225.4 parts by mass of alumina filler (AA-18: 148.76 parts by mass (66% by volume), AA-3: 54 .10 parts by mass (24% by volume), AA-04: 22.54 parts by mass (10% by volume)), 2.65 parts by mass of REB122-4, 0.19 parts by mass of TPP, and 0.09 of KBM-573.
  • a total of 42.37 parts by mass (MEK: 35.82 parts by mass, CHN: 6.55 parts by mass) of 24 parts by mass and an organic solvent were mixed to obtain an epoxy resin varnish as an epoxy resin composition containing an organic solvent.
  • the density of the mixture of the resin monomer A and the curing agent 3 is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3
  • the alumina filler with respect to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler The ratio was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • the density of the mixture of YL6121H a curing agent 3 1.20 g / cm 3, and 3.97 g / cm 3 density of the alumina filler as, the proportion of alumina filler to the total volume of the curing agent and the alumina filler and epoxy resin monomer was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • resin monomer C 18.25 parts by mass, curing agent 3 11.26 parts by mass, alumina filler in total 225.4 parts by mass (AA-18: 148.76 parts by mass (66% by volume), AA-3: 54.10 parts by mass (24% by volume), AA-04: 22.54 parts by mass (10% by volume)), 0.19 parts by mass of TPP,
  • As an epoxy resin composition containing an organic solvent 0.24 parts by weight of KBM-573 and a total of 54.06 parts by weight of an organic solvent (MEK: 44.77 parts by weight, CHN: 9.29 parts by weight) are mixed. To obtain a sheet resin varnish.
  • the density of the mixture of the resin monomer C and the curing agent 3 is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3
  • the alumina filler with respect to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler The ratio was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • the density of the mixture of resin monomer A and TD-2131 is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3
  • the alumina filler with respect to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler The ratio was calculated to be 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.
  • the density of the mixture of resin monomer A and catechol is 1.20 g / cm 3
  • the density of the alumina filler is 3.97 g / cm 3
  • the ratio of the alumina filler to the total volume of the epoxy resin monomer, the curing agent, and the alumina filler is The calculated volume was 74% by volume.
  • a semi-cured epoxy resin composition and a cured epoxy resin composition were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above. The results are shown in Table 1.

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WO2016098709A1 (ja) * 2014-12-15 2016-06-23 日立化成株式会社 エポキシ樹脂組成物、樹脂シート、プリプレグ、積層板、エポキシ樹脂組成物の製造方法、及び硬化体
JPWO2014021427A1 (ja) * 2012-08-02 2016-07-21 学校法人早稲田大学 金属ベースプリント配線板
WO2017010403A1 (ja) * 2015-07-10 2017-01-19 日立化成株式会社 エポキシ樹脂成形材料、成形物及び硬化物
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WO2018070051A1 (ja) * 2016-10-14 2018-04-19 日立化成株式会社 エポキシ樹脂、エポキシ樹脂組成物、エポキシ樹脂硬化物及び複合材料
JPWO2019172342A1 (ja) * 2018-03-06 2021-03-18 昭和電工マテリアルズ株式会社 プリプレグ、積層板、多層プリント配線板、半導体パッケージ及び樹脂組成物、並びに、プリプレグ、積層板及び多層プリント配線板の製造方法

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KR102539483B1 (ko) * 2015-01-29 2023-06-02 가부시끼가이샤 레조낙 에폭시 수지 조성물, 반경화 에폭시 수지 조성물, 수지 시트 및 프리프레그
WO2016190260A1 (ja) * 2015-05-22 2016-12-01 日立化成株式会社 エポキシ樹脂組成物、熱伝導材料前駆体、ｂステージシート、プリプレグ、放熱材料、積層板、金属基板、及びプリント配線板
JP6989486B2 (ja) * 2016-02-25 2022-01-05 昭和電工マテリアルズ株式会社 エポキシ樹脂成形材料、成形物、成形硬化物、及び成形硬化物の製造方法
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