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WO2017122350A1 - Composition de résine époxy, précurseur de matériau thermoconducteur, feuille au stade b, préimprégné, matériau de dissipation de chaleur, plaque stratifiée, substrat métallique, et carte de circuit imprimé - Google Patents

Composition de résine époxy, précurseur de matériau thermoconducteur, feuille au stade b, préimprégné, matériau de dissipation de chaleur, plaque stratifiée, substrat métallique, et carte de circuit imprimé Download PDF

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Publication number
WO2017122350A1
WO2017122350A1 PCT/JP2016/051144 JP2016051144W WO2017122350A1 WO 2017122350 A1 WO2017122350 A1 WO 2017122350A1 JP 2016051144 W JP2016051144 W JP 2016051144W WO 2017122350 A1 WO2017122350 A1 WO 2017122350A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
group
boron nitride
cured product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/051144
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English (en)
Japanese (ja)
Inventor
竹澤　由高
優香 吉田
士輝 宋
慎吾 田中
房郎 北條
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Publication date
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Priority to JP2017561488A priority Critical patent/JPWO2017122350A1/ja
Priority to PCT/JP2016/051144 priority patent/WO2017122350A1/fr
Publication of WO2017122350A1 publication Critical patent/WO2017122350A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C08J5/249—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • 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
    • 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

Definitions

  • the present invention relates to an epoxy resin composition, a heat conductive material precursor, a B stage sheet, a prepreg, a heat dissipation material, a laminated board, a metal board, and a printed wiring board.
  • an epoxy resin is widely used as an insulating material from the viewpoint of high withstand voltage and easy molding.
  • a method for increasing the thermal conductivity of an epoxy resin for example, in JP-A-11-323162, it is effective to use a liquid crystalline epoxy resin obtained by polymerizing a resin composition containing a monomer having a highly oriented mesogenic group. It is described that there is.
  • a method of adding an insulating filler having a high thermal conductivity and an insulating property is generally used.
  • the insulating filler having high thermal conductivity include boron nitride particles, aluminum nitride particles, and alumina particles.
  • an epoxy resin composition capable of forming a cured product having high thermal conductivity, a thermal conductive material precursor, a B stage sheet and a prepreg, and a heat dissipation material having high thermal conductivity, a laminate A board, a metal substrate, and a printed wiring board are provided.
  • X represents a single bond or at least one linking group selected from the group (I) consisting of the following divalent groups.
  • Y independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aliphatic alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, or an acetyl group.
  • Show. n independently represents an integer of 0 to 4.
  • k represents an integer of 0 to 7.
  • m represents an integer of 0 to 8.
  • l represents an integer of 0 to 12.
  • ⁇ 2> The epoxy resin composition according to the above ⁇ 1>, which has a periodic structure in which the length of one cycle is 2 nm to 3 nm.
  • ⁇ 3> The epoxy resin composition according to ⁇ 2>, wherein a half width 2 ⁇ of a peak derived from the periodic structure in X-ray diffraction is 0.2 degrees or less.
  • ⁇ 4> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the boron nitride particles is 20% by mass to 95% by mass in the total solid content.
  • ⁇ 5> Further comprising alumina particles, wherein the content of the alumina particles is 5% by mass to 70% by mass with respect to the total amount of the boron nitride particles and the alumina particles.
  • the epoxy resin composition according to any one of the above.
  • a heat conductive material precursor which is a semi-cured product of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 5>.
  • a half-value width 2 ⁇ of a peak derived from the periodic structure in X-ray diffraction is 0.2 degrees or less.
  • a B stage sheet which is a sheet-like semi-cured product of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 5>.
  • ⁇ 12> a fiber base material;
  • a heat dissipation material which is a cured product of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 5>.
  • a substrate comprising the epoxy resin composition according to any one of ⁇ 1> to ⁇ 5>, provided on the adherend, or any one of ⁇ 9> to ⁇ 11>.
  • Metal foil A metal plate, The resin layer comprising the epoxy resin composition according to any one of the above ⁇ 1> to ⁇ 5>, which is disposed between the metal foil and the metal plate, and any of the above ⁇ 9> to ⁇ 11> A cured layer of at least one resin-containing layer selected from the group consisting of the B stage sheet according to claim 1 and the prepreg according to ⁇ 12>, A metal substrate.
  • a metal plate The resin layer comprising the epoxy resin composition according to any one of ⁇ 1> to ⁇ 5>, which is disposed between the wiring layer and the metal plate, and any of ⁇ 9> to ⁇ 11>
  • a printed wiring board having:
  • an epoxy resin composition capable of forming a cured product having high thermal conductivity, a thermal conductive material precursor, a B stage sheet and a prepreg, and a heat dissipation material having high thermal conductivity, a laminated plate, a metal substrate, and A printed wiring board is provided.
  • FIG. 2 is an X-ray diffraction (XRD) spectrum of the cured epoxy resin of Example 1.
  • FIG. 2 is an X-ray diffraction (XRD) spectrum of a cured epoxy resin of Comparative Example 1.
  • FIG. 1 is an X-ray diffraction (XRD) spectrum of a cured epoxy resin of Comparative Example 1.
  • a numerical range indicated 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 is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • 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. .
  • the term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view.
  • the term “stack” indicates that the layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
  • the average thickness (also referred to as the average thickness) of a layer or a laminate is a value given as an arithmetic average value obtained by measuring the thickness of five layers of the target layer or laminate.
  • the thickness of the layer or laminate can be measured using a micrometer or the like.
  • the thickness of a layer or a laminate can be directly measured, it is measured using a micrometer.
  • the thickness of one layer constituting a part of the laminate or the total thickness of a plurality of layers it is measured by observing a cross section parallel to the lamination direction of the laminate using an electron microscope. To do.
  • 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 upper limit value or the lower limit value described in one numerical range is replaced with the upper limit value or the lower limit value of another numerical range described. May be. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the epoxy resin composition includes boron nitride particles (hereinafter also referred to as “specific boron nitride particles”) having a half-value width 2 ⁇ of a peak derived from the (004) plane in X-ray diffraction (XRD) of 0.5 degrees or less.
  • a curing agent and a liquid crystalline epoxy monomer represented by the following general formula (1) hereinafter also referred to as “specific liquid crystalline epoxy monomer”.
  • the epoxy resin composition may further contain other components.
  • X represents a single bond or at least one linking group selected from group (I) consisting of the following divalent groups.
  • Y independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aliphatic alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, or an acetyl group. Show.
  • n represents an integer of 0 to 4.
  • k represents an integer of 0 to 7.
  • m represents an integer of 0 to 8.
  • l represents an integer of 0 to 12.
  • the connecting direction of the bond of each divalent group may be any.
  • the orientation of the liquid crystalline epoxy resin that is a polymer of the specific liquid crystalline epoxy monomer is suppressed from being inhibited by the specific boron nitride particles, and the cured product of the epoxy resin composition It is thought that the thermal conductivity in the is improved.
  • the components of the epoxy resin composition will be described in detail.
  • the epoxy resin composition contains boron nitride particles having a half width 2 ⁇ of a peak derived from the (004) plane in X-ray diffraction (XRD) of 0.5 degrees or less.
  • the specific boron nitride particles are not particularly limited as long as the half-value width 2 ⁇ of the peak derived from the (004) plane in X-ray diffraction (XRD) is 0.5 degrees or less, and usually used boron nitride particles Can be appropriately selected and used.
  • the half width 2 ⁇ of the peak derived from the (004) plane of the boron nitride particles in X-ray diffraction (XRD) is preferably 0.45 degrees or less. This is because by increasing the crystallinity of the boron nitride particles, the regularity of the boron nitride crystal itself is increased, and the regularity of the structure of the specific liquid crystalline epoxy monomer adjacent to the crystal, that is, the orientation is improved. it is conceivable that.
  • the half width 2 ⁇ of the peak derived from the (004) plane of the boron nitride particles in the present specification is determined using the wide-angle X-ray diffractometer (for example, “RINT2500HL” manufactured by Rigaku Corporation) under the following conditions.
  • X-ray diffraction is performed using a semi-cured product or a cured product of the epoxy resin composition as a measurement sample, and the obtained value is calculated by the following Bragg equation.
  • ⁇ X-ray source Cu ⁇ X-ray output: 50 kV, 250 mA -Divergence slit (DS): 1.0 degree-Scattering slit (SS): 1.0 degree-Receiving slit (RS): 0.3 mm ⁇ Scanning speed: 1.0 degree / min
  • the specific boron nitride particles may be any of single crystal particles, single crystal aggregated particles, polycrystalline particles, polycrystalline aggregated particles, and the like.
  • the crystal structure of the specific boron nitride particles may be any of hexagonal, cubic and wurtzite structures. From the viewpoint of use as a filler for a heat dissipation material, the crystal structure of the specific boron nitride particles is preferably a hexagonal crystal.
  • the volume average particle diameter of the specific boron nitride particles is preferably 0.01 ⁇ m to 1 mm from the viewpoint of use as a filler of the heat dissipation material.
  • the volume average particle diameter of the specific boron nitride particles is more preferably from 0.1 ⁇ m to 100 ⁇ m, and further preferably from 0.5 ⁇ m to 50 ⁇ m, from the viewpoint of highly filling the specific boron nitride particles.
  • the volume average particle diameter of the specific boron nitride particles is measured using a laser diffraction method.
  • the laser diffraction method can be performed using a laser diffraction scattering particle size distribution measuring apparatus (for example, Beckman Coulter, Inc., “LS230”).
  • the volume average particle diameter of the boron nitride particles in the epoxy resin composition is measured using a laser diffraction / scattering particle size distribution analyzer after extracting the boron nitride particles from the epoxy resin composition.
  • the volume average particle diameter of the boron nitride particles contained in the epoxy resin composition can be measured by the following method. First, boron nitride particles are extracted from the epoxy resin composition using an organic solvent, nitric acid, aqua regia, etc., and sufficiently dispersed with an ultrasonic disperser or the like to prepare a dispersion.
  • the particle diameter (D50) that is 50% cumulative is the volume average particle size. Calculate as diameter.
  • the volume average particle diameter of the specific boron nitride particles can also be measured by a 3D CT method or a method using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the volume average particle diameter of specific boron nitride particles can be measured by using Shimadzu Corporation, inspexio SMX-225CT. Specifically, a semi-cured product or cured product of an epoxy resin composition, or a sample obtained by cutting a resin sheet or a cured product thereof into a 10 mm square is fixed to a sample stage, irradiated with X-rays there, and photographed three-dimensional From the image, the volume average particle diameter of the specific boron nitride particles can be calculated by analyzing the ratio of the resin, the specific boron nitride particles, and the like by image analysis and calculating the ratio of each component.
  • volume average particle diameter of specific boron nitride particles is obtained by a method using SEM
  • a focused ion beam mounted scanning electron microscope SEM FIB
  • SEM FIB focused ion beam mounted scanning electron microscope
  • the epoxy resin composition was set to be inclined with respect to the cross-section while performing the cross-section processing by injecting a Ga ion beam perpendicularly to the semi-cured or cured product of the epoxy resin composition or the resin sheet or the cured product thereof. By observing with SEM, the volume average particle diameter can be determined.
  • Imaging is preferably performed at a processing pitch of 1 nm to 100 nm, and the pitch may be adjusted according to the size of the object to be imaged.
  • the production method of the specific boron nitride particles is not particularly limited as long as the half width 2 ⁇ of the peak derived from the (004) plane in X-ray diffraction (XRD) is 0.5 degrees or less. It may be formed by any manufacturing method such as a method or a gas phase reaction method.
  • the content of the specific boron nitride particles in the specific epoxy resin composition is not particularly limited.
  • the content of the specific boron nitride particles is preferably 20% by mass to 95% by mass in the total solid content in the epoxy resin composition from the viewpoint of viscosity adjustment, and 30% by mass from the viewpoint of thermal conductivity.
  • the content is more preferably 90% by mass, and further preferably 40% by mass to 85% by mass.
  • solid content in an epoxy resin composition means the residue which removed the volatile component from the structural component of the resin composition.
  • the epoxy resin composition contains a specific liquid crystalline epoxy monomer represented by the following general formula (1).
  • X represents a single bond or at least one linking group selected from group (I) consisting of the following divalent groups.
  • Y independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aliphatic alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, or an acetyl group.
  • Show. n independently represents an integer of 0 to 4.
  • k represents an integer of 0 to 7.
  • m represents an integer of 0 to 8.
  • l represents an integer of 0 to 12.
  • the connecting direction of the bond of each divalent group may be any.
  • the specific liquid crystalline epoxy monomer in this specification is a monomer having a so-called mesogenic group.
  • a specific liquid crystalline epoxy monomer forms a cured product with a curing agent, it is derived from a mesogenic group (biphenyl group, terphenyl group, terphenyl analog group, a group in which these are connected by an azomethine group or an ester group, etc.) in the cured product.
  • Higher order structure also referred to as a periodic structure
  • the higher order structure means a state in which molecules are aligned after the epoxy resin composition is cured, for example, a state in which a crystal structure or a liquid crystal structure is present in the cured product. .
  • the cured product of the epoxy resin composition tends to have a high thermal conductivity.
  • the reason can be considered as follows, for example.
  • the specific liquid crystalline epoxy monomer represented by the general formula (1) forms a cured product together with a curing agent, a highly ordered higher order structure derived from the mesogenic group of the specific liquid crystalline epoxy monomer is formed in the cured product.
  • scattering of phonon conduction which is a heat conductive medium in the insulating resin, can be suppressed, and thereby high thermal conductivity can be achieved.
  • the presence of the filler hinders formation of a highly ordered higher-order structure by the liquid crystalline epoxy resin.
  • X in the general formula (1) is preferably at least one linking group selected from the group (II) consisting of the following divalent groups.
  • X in the general formula (1) is more preferably at least one linking group selected from the group consisting of the following divalent linking groups.
  • Y in the general formula (1) independently represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an aliphatic alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. It is preferably a nitro group or an acetyl group, more preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group or a chlorine atom, and even more preferably a methyl group or an ethyl group.
  • N in the general formula (1) are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.
  • k is preferably an integer of 0 to 3, and more preferably 0 or 1.
  • m is preferably an integer of 0 to 4, and more preferably 0 or 1.
  • l is preferably an integer of 0 to 4, more preferably 0 or 1.
  • X is a single bond or at least one linking group selected from the group (II) consisting of the above divalent group, and Y is independent.
  • Y is independent.
  • an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an aliphatic alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, or an acetyl group, and n is It is preferably a liquid crystalline epoxy monomer that is an integer of 0 to 2, k is an integer of 0 to 3, m is an integer of 0 to 4, and l is an integer of 0 to 4.
  • the specific liquid crystalline epoxy monomer is represented by the general formula (1), wherein X is a single bond or at least one linking group selected from the group (II) consisting of the above divalent group, and each Y is independently methyl
  • a liquid crystalline epoxy which is a group, an ethyl group, a methoxy group, an ethoxy group or a chlorine atom, n is 0 or 1, k is 0 or 1, m is 0 or 1, and l is 0 or 1 More preferably, it is a monomer.
  • the temperature range in which the liquid crystal phase is expressed is 25 ° C. or more, the orientation of the liquid crystalline epoxy monomer is improved, and the thermal conductivity of the cured product is improved.
  • the liquid crystalline epoxy monomer represented by the general formula (1) can be produced by a known method, and is described in Japanese Patent No. 4619770, Japanese Patent Application Laid-Open No. 2011-98952, Japanese Patent Application Laid-Open No. 2011-74366, and the like. Refer to the manufacturing method.
  • the specific liquid crystalline epoxy monomer in the epoxy resin composition may be partially polymerized with a curing agent or the like to form a prepolymer.
  • the specific liquid crystalline epoxy monomer is generally easily crystallized and often has low solubility in a solvent.
  • crystallization of the specific liquid crystalline epoxy monomer tends to be suppressed. For this reason, when the specific liquid crystalline epoxy monomer is prepolymerized, the moldability of the epoxy resin composition tends to be improved.
  • the content of the specific liquid crystalline epoxy monomer in the epoxy resin composition is 3% by volume to 30% by volume with respect to the total solid content in the epoxy resin composition from the viewpoints of moldability, adhesiveness, and thermal conductivity. It is preferably 5% by volume to 25% by volume.
  • volume-based content of the specific liquid crystalline epoxy monomer with respect to the total solid content is a value determined by the following formula.
  • Aw Mass composition ratio (% by mass) of boron nitride particles
  • Bw mass composition ratio (mass%) of the specific liquid crystalline epoxy monomer
  • Cw mass composition ratio (% by mass) of curing agent
  • Dw mass composition ratio (% by mass) of other optional components (excluding solvent)
  • Ad Specific gravity of boron nitride particles
  • Bd Specific gravity of specific liquid crystalline epoxy monomer
  • Cd Specific gravity of curing agent
  • Dd Specific gravity of other optional components (excluding solvent)
  • the epoxy resin composition preferably has a periodic structure in which the length of one cycle is 2 nm to 3 nm. When the length of one cycle is 2 nm to 3 nm, higher thermal conductivity can be exhibited.
  • the length of one period in the periodic structure is determined using a semi-cured or cured product of the epoxy resin composition as a measurement sample using a wide-angle X-ray diffractometer (for example, “RINT2500HL” manufactured by Rigaku Corporation) under the following conditions. It is obtained by performing X-ray diffraction and converting the diffraction angle obtained thereby by the following Bragg equation.
  • a wide-angle X-ray diffractometer for example, “RINT2500HL” manufactured by Rigaku Corporation
  • ⁇ X-ray source Cu ⁇ X-ray output: 50 kV, 250 mA -Divergence slit (DS): 1.0 degree-Scattering slit (SS): 1.0 degree-Receiving slit (RS): 0.3 mm ⁇ Scanning speed: 1.0 degree / min
  • the epoxy resin composition preferably has a half width 2 ⁇ of a peak derived from a periodic structure in X-ray diffraction of 0.2 ° or less, more preferably 0.15 ° or less, and 0.13 ° or less. More preferably it is. It shows that the regularity of the periodic structure is higher as the half width is narrower.
  • XRD peak the full width at half maximum 2 ⁇ of a peak derived from a periodic structure in X-ray diffraction
  • the epoxy resin composition includes a curing agent.
  • the curing agent in the present specification is not particularly limited as long as it is a compound capable of curing reaction with a specific epoxy resin monomer.
  • Specific examples of the curing agent include amine curing agents, acid anhydride curing agents, phenol curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. These may be used alone or in combination of two or more. From the viewpoint of forming a periodic structure of the semi-cured product or cured product of the epoxy resin composition, an amine curing agent or a phenol curing agent is preferable, and a phenol curing agent is more preferable.
  • Examples of amine curing agents include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino-3,3′-dimethoxybiphenyl, 4, Examples thereof include 4′-diaminophenylbenzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 1,8-diaminonaphthalene and the like. Among these, 1,5-diaminonaphthalene is preferable from the viewpoint of forming a higher order structure. From the viewpoint of cost and handleability, 4,4'-diaminodiphenylmethane is preferred.
  • low molecular phenol compounds and phenol resins obtained by novolacizing them can be used as the phenol curing agent.
  • low molecular weight phenol compounds include monofunctional phenol compounds such as phenol, o-cresol, m-cresol, and p-cresol, bifunctional phenol compounds such as catechol, resorcinol, and hydroquinone, 1,2,3-trihydroxybenzene , Trifunctional phenol compounds such as 1,2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene.
  • a phenol novolac resin obtained by connecting these low molecular phenol compounds with a methylene chain or the like to form a novolac can be used as a curing agent.
  • phenol curing agent bifunctional phenol compounds such as catechol, resorcinol and hydroquinone are preferable from the viewpoint of thermal conductivity.
  • a phenol novolac resin in which these bifunctional phenol compounds are linked by a methylene chain is preferable.
  • Specific examples of phenol novolak resins include two types of resins such as cresol novolak resins, catechol novolak resins, resorcinol novolak resins, hydroquinone novolak resins and other novolac resins, catechol resorcinol novolak resins, and resorcinol hydroquinone novolak resins. Or the resin etc. which made the more phenol compound novolak-ized can be mentioned.
  • a curing accelerator may be used in combination as necessary.
  • the epoxy resin composition tends to be cured sufficiently.
  • the kind in particular of hardening accelerator is not restrict
  • curing agent in an epoxy resin composition can be suitably set in consideration of the kind of hardening
  • the chemical equivalent of the curing agent is preferably 0.005 equivalents to 5 equivalents, more preferably 0.01 equivalents to 3 equivalents, relative to 1 mol of the epoxy group in the specific liquid crystalline epoxy monomer. More preferably, it is 0.5 to 1.5 equivalents.
  • the content of the curing agent is 0.005 equivalent or more with respect to 1 mol of the epoxy group, the curing rate of the specific liquid crystalline epoxy monomer tends to be further improved.
  • curing agent is 5 equivalent or less with respect to 1 mol of epoxy groups.
  • the chemical equivalent in this specification represents the number of moles of the hydroxyl group of the phenol curing agent with respect to 1 mole of the epoxy group when, for example, a phenol curing agent is used as the curing agent.
  • the epoxy resin composition may contain other components such as a solvent as necessary.
  • the epoxy resin composition may contain a solvent for dissolving the epoxy resin or the curing agent when the epoxy resin or the curing agent is solid, or for reducing the viscosity when the epoxy resin composition is a liquid.
  • solvents include acetone, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, ethyl ether, ethylene glycol monoethyl ether, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, methyl acetate, cyclohexanol.
  • the epoxy resin composition may contain other boron nitride particles other than the specific boron nitride particles having a half width 2 ⁇ of a peak derived from the (004) plane in X-ray diffraction (XRD) of 0.5 degrees or less.
  • the content of other boron nitride particles is preferably 0% by mass to 50% by mass, and preferably 0% by mass to 20% by mass with respect to the total amount of the specific boron nitride particles and other boron nitride particles. More preferred.
  • the epoxy resin composition comprises ceramic particles other than specific boron nitride particles having a half-value width 2 ⁇ of a peak derived from the (004) plane in X-ray diffraction (XRD) of 0.5 degrees or less, a coupling agent, a dispersant, and an elastomer. Etc. may be contained. Ceramic particles other than the specific boron nitride particles whose half width 2 ⁇ of the peak derived from the (004) plane in X-ray diffraction (XRD) is 0.5 degrees or less include alumina particles, silica particles, magnesium oxide particles, aluminum nitride Examples thereof include particles and silicon nitride particles, and alumina particles are preferred.
  • the epoxy resin composition may or may not contain alumina particles.
  • the content of alumina particles with respect to the total amount of boron nitride particles (specific boron nitride particles and other boron nitride particles) and alumina particles is 5 mass% to 70 mass%. It is preferably 10% by mass to 50% by mass.
  • the volume average particle diameter of the alumina particles is preferably 0.01 ⁇ m to 1 mm from the viewpoint of use as a filler of the heat dissipation material, and more preferably 0.1 ⁇ m to 100 ⁇ m from the viewpoint of high filling of the alumina particles. .
  • the alumina particles are preferably alumina particles having high crystallinity, and more preferably ⁇ -alumina particles.
  • the volume average particle diameter of the alumina particles is measured using a laser diffraction method.
  • the laser diffraction method can be performed by a method similar to the measurement of the volume average particle diameter of the boron nitride particles described above using a laser diffraction scattering particle size distribution measuring apparatus (for example, Beckman Coulter, Inc., “LS230”). it can.
  • Method for producing epoxy resin composition As a manufacturing method of an epoxy resin composition, the manufacturing method of the resin composition performed normally can be especially used without a restriction
  • an epoxy resin composition is obtained by mixing other components as required in a solution obtained by dissolving or dispersing specific boron nitride particles, liquid crystalline epoxy monomer and curing agent in an appropriate solvent. be able to.
  • the epoxy resin composition In the epoxy resin composition, the orientation of the specific liquid crystalline epoxy monomer is high, and the semi-cured product or cured product of the epoxy resin composition tends to be excellent in thermal conductivity. Therefore, the epoxy resin composition can be suitably used as a heat-dissipating material for heat-generating electronic components (for example, IC (Integrated Circuit) chips or printed wiring boards) of various electric devices and electronic devices. Specifically, the epoxy resin composition can be used as a heat conductive material precursor such as a B stage sheet or a prepreg, a heat dissipation material such as a laminated board, a metal board, or a printed wiring board.
  • a heat conductive material precursor such as a B stage sheet or a prepreg
  • a heat dissipation material such as a laminated board, a metal board, or a printed wiring board.
  • the heat conductive material precursor of this embodiment is a semi-cured product of the epoxy resin composition of this embodiment.
  • the heat conductive material precursor of this embodiment it is possible to obtain a heat dissipating material that is excellent in handleability and has high heat conductivity.
  • Examples of the heat conductive material precursor include a B-stage sheet that is a sheet-like semi-cured product of the epoxy resin composition of the present embodiment, a fiber base material, and the epoxy resin composition of the present embodiment impregnated in the fiber base material.
  • Examples thereof include a prepreg having a semi-cured product.
  • the semi-cured product of the epoxy resin composition preferably has a periodic structure in which the length of one cycle is 2 nm to 3 nm.
  • the length of one cycle is 2 nm to 3 nm
  • the semi-cured product of the epoxy resin composition tends to exhibit higher thermal conductivity.
  • the half-cured product of the epoxy resin composition preferably has an X-ray diffraction (XRD) peak half-value width 2 ⁇ derived from the periodic structure of 0.2 degrees or less.
  • XRD X-ray diffraction
  • the half width of the XRD peak derived from the periodic structure is 0.2 degrees or less, the semi-cured product of the epoxy resin composition tends to exhibit higher thermal conductivity.
  • the B stage sheet and the prepreg will be described as examples of the heat conductive material precursor, the heat conductive material precursor is not limited thereto.
  • the B stage sheet of the present embodiment is a sheet-like semi-cured product of the epoxy resin composition of the present embodiment.
  • the B stage sheet of the present embodiment is obtained, for example, by molding the epoxy resin composition of the present embodiment into a sheet shape and semi-curing it.
  • a B stage sheet having excellent thermal conductivity after curing can be obtained.
  • “semi-cured” refers to a state generally referred to as a B-stage state.
  • the viscosity at a normal temperature (25 ° C.) is 10 4 Pa ⁇ s to 10 5 Pa ⁇ s, whereas at 100 ° C.
  • the B stage is defined in JIS K 6900: 1994 or ISO 472: 1988.
  • the viscosity can be measured with a torsional dynamic viscoelasticity measuring device or the like.
  • the B stage sheet can be produced, for example, by applying (applying) the epoxy resin composition of the present embodiment on a support, drying to produce a resin sheet, and semi-curing the resin sheet.
  • a commonly used method can be appropriately selected without particular limitation. Specifically, a comma coating method, a die coating method, a dip coating method, or the like can be given as a method for applying the epoxy resin composition.
  • a box-type hot air dryer or the like can be used for batch processing, and a multi-stage hot air dryer or the like can be used for continuous processing with a coating machine.
  • a hot air dryer from the viewpoint of preventing swelling of the epoxy resin composition, it includes a step of heat treatment with hot air in a temperature range lower than the boiling point of the solvent. It is preferable.
  • the method for semi-curing the resin sheet is not particularly limited, and a commonly used method can be appropriately selected.
  • the epoxy resin composition can be semi-cured by heat-treating the resin sheet.
  • the temperature range for semi-curing the resin sheet can be appropriately selected according to the type of liquid crystalline epoxy monomer contained in the epoxy resin composition. From the viewpoint of the strength of the B stage sheet, it is preferable to proceed the curing reaction slightly by heat treatment, and the temperature range of the heat treatment is preferably 80 ° C. to 180 ° C., more preferably 100 ° C. to 160 ° C. Moreover, there is no restriction
  • the heat treatment time for semi-curing is preferably 1 minute or longer and within 30 minutes, and more preferably 1 minute or longer and within 10 minutes.
  • Pressurization may be performed during the heat treatment for semi-curing, and the pressurization conditions are not particularly limited. Usually, it is preferable to pressurize in the range of 0.5 MPa to 15 MPa and pressurize in the range of 1 MPa to 10 MPa. A vacuum press or the like is preferably used for the heat treatment and the pressure treatment.
  • the average thickness of the B stage sheet can be appropriately selected according to the purpose, and can be, for example, 50 ⁇ m to 500 ⁇ m.
  • the average thickness of the B stage sheet is preferably 80 ⁇ m to 300 ⁇ m from the viewpoints of thermal conductivity, electrical insulation, and flexibility.
  • the average thickness of the B stage sheet is a value given as an arithmetic average value obtained by measuring the thickness of five points of the target B stage sheet using a micrometer or the like.
  • a B-stage sheet can also be produced by hot pressing while laminating two or more resin sheets (a sheet-like molded product of an epoxy resin composition and before curing).
  • the B stage sheet is preferably a sheet-like semi-cured product of an epoxy resin composition having a periodic structure with a period of 2 nm to 3 nm.
  • the B stage sheet tends to exhibit higher thermal conductivity.
  • the B stage sheet preferably has an X-ray diffraction (XRD) peak half-value width 2 ⁇ derived from the periodic structure of 0.2 degrees or less. When the half width 2 ⁇ of the XRD peak derived from the periodic structure is 0.2 degrees or less, the B stage sheet can exhibit higher thermal conductivity.
  • XRD X-ray diffraction
  • the prepreg of this embodiment has a fiber base material and a semi-cured product of the epoxy resin composition of this embodiment impregnated in the fiber base material.
  • the prepreg may have other layers such as a protective film as necessary.
  • the semi-cured product of the epoxy resin composition includes the specific boron nitride particles according to the present embodiment, a prepreg capable of forming a cured product having excellent thermal conductivity can be obtained.
  • the fiber substrate constituting the prepreg is not particularly limited as long as it is a fiber substrate used when producing a metal foil-clad laminate or a multilayer printed wiring board.
  • fiber base materials such as a woven fabric and a nonwoven fabric, are mentioned.
  • boron nitride particles may be clogged in the gaps between the fibers, making it difficult to impregnate the epoxy resin composition.
  • the opening is preferably at least 5 times the volume average particle diameter of the boron nitride particles.
  • fiber base materials include: inorganic fibers such as glass, alumina, boron, silica alumina glass, silica glass, tyrano fiber, silicon carbide, silicon nitride, zirconia; aramid, polyether ether ketone, polyether imide, poly Examples thereof include organic fibers such as ether sulfone, carbon, and cellulose; and mixed fiber base materials thereof.
  • a glass fiber woven fabric is preferably used.
  • the thickness of the fiber base material is not particularly limited, and is preferably 30 ⁇ m or less from the viewpoint of imparting better flexibility, and more preferably 15 ⁇ m or less from the viewpoint of impregnation property of the epoxy resin composition.
  • the lower limit of the thickness of the fiber substrate is not particularly limited, and is usually about 5 ⁇ m.
  • the impregnation ratio of the epoxy resin composition is preferably 50% by mass to 99.9% by mass with respect to the total mass of the fiber base material and the epoxy resin composition.
  • the prepreg can be produced, for example, by impregnating a fiber base material with an epoxy resin composition prepared in the same manner as described above and removing the solvent by heating at 80 ° C. to 180 ° C.
  • 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 0.7% by mass or less.
  • the solvent residual rate is obtained from the mass change before and after drying when the prepreg is cut into a 40 mm square and dried in a thermostat preheated to 190 ° C. for 2 hours.
  • the drying time for removing the solvent by heat treatment is not particularly limited.
  • limiting in particular in the method of impregnating a fiber base material with an epoxy resin composition For example, the method of providing (application
  • a vertical coating method in which a fiber base material is pulled through an epoxy resin composition a horizontal coating method in which an epoxy resin composition is applied on a support film and then impregnated by pressing the fiber base material, etc. Can do. From the viewpoint of suppressing the uneven distribution of the thermally conductive filler in the fiber base material, the horizontal coating method is suitable.
  • the epoxy resin composition of the present embodiment impregnated in the fiber base material is semi-cured and is in a B stage state.
  • the B stage state in the prepreg is synonymous with the B stage state in the B stage sheet described above, and the same conditions can be applied to the method of forming the B stage.
  • the prepreg may be used after the surface is smoothed in advance by laminating or sticking to a base material by heat and pressure treatment with a press, a roll laminator or the like.
  • the example of the method of heat-pressing treatment is the same as the method quoted with the above-mentioned B stage sheet.
  • the conditions of the heating temperature and the press pressure in the heat and pressure treatment of the prepreg are the same as the conditions mentioned in the heat treatment and pressure treatment of the B stage sheet.
  • the average thickness of the prepreg can be appropriately selected according to the purpose, and can be, for example, 50 ⁇ m or more and 500 ⁇ m or less.
  • the average thickness of the prepreg is preferably 60 ⁇ m or more and 300 ⁇ m or less from the viewpoint of thermal conductivity and flexibility.
  • the average thickness of the prepreg is a value given as an arithmetic average value obtained by measuring the thicknesses of five points of the target prepreg using a micrometer or the like.
  • the prepreg can be produced by laminating two or more prepregs and hot pressing.
  • the heat dissipation material of this embodiment is a cured product of the epoxy resin composition of this embodiment.
  • Specific examples of the heat dissipation material include a laminated board having a cured product of the epoxy resin composition of the present embodiment, a metal board, a printed wiring board, and the like.
  • the heat dissipation material has excellent thermal conductivity by including the cured product of the epoxy resin composition of the present embodiment.
  • the cured product of the epoxy resin composition preferably has a periodic structure in which the length of one cycle is 2 nm to 3 nm.
  • the length of one cycle is 2 nm to 3 nm
  • the cured product of the epoxy resin composition tends to exhibit higher thermal conductivity.
  • the half width 2 ⁇ of the X-ray diffraction (XRD) peak derived from the periodic structure is 0.2 degrees or less.
  • the half width of the XRD peak derived from the periodic structure is 0.2 degrees or less, the cured product of the epoxy resin composition tends to exhibit higher thermal conductivity.
  • the laminate in the present embodiment comprises an adherend, a resin layer made of the epoxy resin composition of the present embodiment, a B stage sheet of the present embodiment, and a prepreg of the present embodiment provided on the adherend.
  • adherend examples include metal foil and metal plate.
  • the adherend may be provided on only one side of the cured layer or on 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 1 ⁇ m to 200 ⁇ m, and a suitable thickness can be selected according to the electric power used.
  • metal foil nickel, nickel-phosphorus alloy, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a copper layer of 0.5 ⁇ m to 15 ⁇ m is formed on both surfaces.
  • a composite foil having a three-layer structure provided with a copper layer of 10 ⁇ m to 150 ⁇ m may be used.
  • metal foil a two-layer structure 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 a high thermal conductivity and a large heat capacity.
  • Specific examples of the material for the metal plate include copper, aluminum, iron, alloys used for lead frames, and the like.
  • the metal plate is not particularly limited, and can be appropriately selected from commonly used metal plates.
  • the material can be selected according to the purpose, such as using an aluminum plate when priority is given to weight reduction or workability, and using a copper plate when priority is given to heat dissipation.
  • the average thickness of the metal plate can be appropriately selected depending on the application, and is not particularly limited. From the viewpoint of workability, the thickness of the metal plate 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 used 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 kind of aluminum plate or aluminum alloy plate that is easy to cut and has high workability and excellent strength.
  • the cured layer has a single layer structure having a cured layer of a resin layer made of the epoxy resin composition of the present embodiment, a B stage sheet of the present embodiment, or a resin-containing layer that is a prepreg of the present embodiment. It may be a laminated structure having two or more layers.
  • the hardened layer has a laminated structure of two or more layers, a form having two or more resin layers made of the epoxy resin composition of the present embodiment, a form having two or more B stage sheets of the present embodiment, and the present embodiment Any of the forms having two or more prepregs may be used.
  • the laminated board in the present embodiment is formed by, for example, applying the epoxy resin composition of the present embodiment on an adherend to form a resin layer, heat-treating and pressurizing the resin layer, and curing the resin layer. It is obtained by making it adhere to an adherend.
  • the curing method for curing the resin layer, the B stage sheet and the prepreg made of the epoxy resin composition is not particularly limited.
  • the heating temperature in the heat treatment and pressure treatment is not particularly limited.
  • the heating temperature is usually in the range of 100 ° C to 250 ° C, and preferably in the range of 130 ° C to 230 ° C.
  • the pressurization conditions in heat processing and pressurization processing are not specifically limited.
  • the pressurizing condition is usually in the range of 1 MPa to 10 MPa, and preferably in the range of 1 MPa to 5 MPa.
  • a vacuum press machine etc. are used suitably for heat processing and pressurization processing.
  • the average thickness of the cured layer of the resin layer made of the epoxy resin composition or the cured layer of the resin-containing layer that is a B stage sheet or prepreg is preferably 500 ⁇ m or less, more preferably 50 ⁇ m to 300 ⁇ m, and more preferably 60 ⁇ m to 300 ⁇ m. More preferably.
  • the average thickness is 500 ⁇ m or less, the flexibility is excellent, and the generation of cracks during bending is suppressed, and when the average thickness is 300 ⁇ m or less, the generation of cracks during bending tends to be further suppressed. It is in. Moreover, it exists in the tendency for workability
  • the average thickness of the cured layer is a value given as an arithmetic average value obtained by measuring the thickness of five points of the cured layer of the target laminate by using a micrometer or the like.
  • the metal substrate of the present embodiment includes a metal foil, a metal plate, a resin layer made of the epoxy resin composition of the present embodiment, disposed between the metal foil and the metal plate, and a B stage sheet of the present embodiment. And a cured layer of at least one resin-containing layer selected from the group consisting of the prepregs of the present embodiment.
  • 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 1 ⁇ m to 200 ⁇ m, and a suitable thickness can be selected according to the electric power used.
  • metal foil nickel, nickel-phosphorus alloy, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a copper layer of 0.5 ⁇ m to 15 ⁇ m is formed on both surfaces.
  • a composite foil having a three-layer structure provided with a copper layer of 10 ⁇ m to 150 ⁇ m may be used, or a two-layer composite foil in which aluminum and a copper foil are combined can also be used.
  • the metal plate is preferably made of a metal material having a high thermal conductivity and a large heat capacity.
  • the metal material include copper, aluminum, iron, alloys used for lead frames, and the like. It does not restrict
  • the material can be selected according to the purpose, such as using an aluminum plate when priority is given to weight reduction or workability, and using a copper plate when priority is given to heat dissipation.
  • the average thickness of the metal plate can be appropriately selected depending on the application, and is not particularly limited. From the viewpoint of workability, the thickness of the metal plate 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 used 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 cured layer has a single layer structure having a cured layer of a resin layer made of the epoxy resin composition of the present embodiment, a B stage sheet of the present embodiment, or a resin-containing layer that is a prepreg of the present embodiment. It may be a laminated structure having two or more layers.
  • the hardened layer has a laminated structure of two or more layers, a form having two or more resin layers made of the epoxy resin composition of the present embodiment, a form having two or more B stage sheets of the present embodiment, and the present embodiment Any of the forms having two or more prepregs may be used.
  • the printed wiring board of this embodiment includes a wiring layer, a metal plate, and a resin layer made of the epoxy resin composition of this embodiment, disposed between the wiring layer and the metal plate, and the B stage of this embodiment.
  • the wiring layer can be manufactured by circuit processing the metal foil on the metal substrate described above.
  • a normal photolithography method can be applied to the circuit processing of the metal foil.
  • Examples of the metal plate include the same metal plate used for the above-mentioned metal substrate, and the preferred embodiment is also the same.
  • Preferable embodiments of the printed wiring board include, for example, the same printed wiring board as described in paragraph No. 0064 of JP2009-214525A and paragraph Nos. 0056 to 0059 of JP2009-275086A. it can.
  • cyclohexane was added to prepare a novolac resin and a solution having a content of 50% by mass to obtain a phenol resin solution.
  • Example 1 Boron nitride particles (Mizushima Alloy Iron Co., Ltd., trade name “HP-40”, hereinafter also referred to as “boron nitride particles 1”) and liquid crystalline epoxy monomer 1 (1- (3-methyl-4-oxiranyl) Methoxyphenyl) -4- (oxiranylmethoxyphenyl) -1-cyclohexene; a liquid crystalline epoxy monomer represented by general formula (1) (hereinafter also referred to as “epoxy monomer 1”), and a curing agent (above A phenol resin), a curing accelerator (triphenylphosphine, Wako Pure Chemical Industries, Ltd.) and a solvent (cyclohexanone, Wako Pure Chemical Industries, Ltd.) were added to prepare an epoxy resin composition.
  • boronitride particles 1 liquid crystalline epoxy monomer 1 (1- (3-methyl-4-oxiranyl) Methoxyphenyl) -4- (oxiranylmethoxypheny
  • the compounding amounts of the liquid crystalline epoxy monomer and the curing agent were adjusted such that the molar ratio of the chemical equivalent of the curing agent to the epoxy group of the liquid crystalline epoxy monomer was 1: 1.
  • the addition amount of the boron nitride particles was adjusted so that the boron nitride content in the epoxy resin composition after curing was 50% by mass.
  • the prepared epoxy resin composition was applied to a 75 ⁇ m thick polyethylene terephthalate (PET) film at a thickness of 300 ⁇ m, and then the epoxy resin composition was sandwiched between different PET films at 140 ° C., 1 MPa for 2 minutes.
  • a B-stage sheet was obtained by vacuum pressing.
  • d is the length of one period
  • ⁇ is the diffraction angle
  • n is the reflection order
  • ⁇ is the X-ray wavelength (0.15406 nm).
  • the PET film on both sides of the obtained B-stage sheet is peeled off, and sandwiched between two sheets of copper foil (Furukawa Electric Co., Ltd., trade name “GTS”) whose surface is roughened, and vacuum-pressed at 180 ° C. It was made to press-fit to copper foil. This was further heat-treated at 140 ° C. for 2 hours and then cured by further heat-treating at 190 ° C. for 2 hours to obtain a sheet-like copper press-cured cured product.
  • GTS copper foil
  • the copper foils on both sides of the obtained copper press-cured cured product were removed by acid etching using a mixed solution of 200 g / L ammonium persulfate and 5 ml / L sulfuric acid to obtain a sheet-shaped epoxy resin cured product.
  • the obtained sheet-like epoxy resin cured product was cut into a 1 cm square and used as a test piece for measuring thermal diffusivity.
  • the thermal diffusivity of the cut specimen was measured using a flash method apparatus (“NETZSCH, nanoflash LFA447” manufactured by Bruker AXS Co., Ltd.). By multiplying the measurement result by the density measured by the Archimedes method and the specific heat measured by the DSC method, the thermal conductivity in the thickness direction of the cured epoxy resin sheet was determined.
  • the diffraction angle derived from the periodic structure of the obtained sheet-like cured epoxy resin was measured in the same manner as in the case of the B stage sheet. From the obtained XRD spectrum, the half width (2 ⁇ ) of the peak derived from the (004) plane of the boron nitride particles was determined. The results are shown in Table 1 and FIG.
  • Example 2 In Example 1, instead of boron nitride particles 1, boron nitride particles (Electrochemical Industry Co., Ltd., trade name “SP-3”, hereinafter also referred to as “boron nitride particles 2”) were used. In the same manner as in Example 1, a B-stage sheet and a sheet-like cured epoxy resin were prepared. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 3 In Example 1, ⁇ -alumina particles (Sumitomo Chemical Co., Ltd., trade name “AA04”) were added, and the content of boron nitride particles 1 in the cured epoxy resin (epoxy resin cured product) was 50 mass%.
  • the epoxy resin composition of Example 3 was obtained in the same manner as in Example 1 except that the epoxy resin composition was prepared so that the content of ⁇ -alumina particles was 20% by mass.
  • Example 1 Using the resulting epoxy resin composition, a B-stage sheet and a sheet-like cured epoxy resin were prepared in the same manner as in Example 1. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 4 In Example 1, boron nitride particles 2 (Electrochemical Industry Co., Ltd., trade name “SP-3”) was added, and the content of boron nitride particles 1 in the cured epoxy resin (cured epoxy resin) was 50.
  • the epoxy resin composition of Example 4 was obtained in the same manner as in Example 1 except that the epoxy resin composition was prepared so that the content of the boron nitride particles 2 was 20% by mass. It was.
  • Example 1 Using the resulting epoxy resin composition, a B-stage sheet and a sheet-like cured epoxy resin were prepared in the same manner as in Example 1. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 5 In Example 1, boron nitride particles 3 (Mitsui Chemicals, Inc., trade name “MBN-250”) was added, and the content of boron nitride particles 1 in the cured epoxy resin (epoxy resin cured product) was 50 mass. %, And the epoxy resin composition of Example 5 was obtained in the same manner as in Example 1 except that the epoxy resin composition was prepared so that the content of boron nitride particles 3 was 20% by mass. .
  • MBN-250 boron nitride particles 3
  • Example 1 Using the resulting epoxy resin composition, a B-stage sheet and a sheet-like cured epoxy resin were prepared in the same manner as in Example 1. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 6 In Example 1, boron nitride particles 2 (Electrochemical Industry Co., Ltd., trade name “SP-3”) and ⁇ -alumina particles (Sumitomo Chemical Co., Ltd., trade name “AA04”) were added and cured.
  • the content of boron nitride particles 1 in the epoxy resin (cured epoxy resin) is 50% by mass
  • the content of boron nitride particles 2 is 10% by mass
  • the content of ⁇ -alumina particles is 10% by mass.
  • An epoxy resin composition of Example 6 was obtained in the same manner as in Example 1 except that the epoxy resin composition was prepared.
  • Example 1 Using the resulting epoxy resin composition, a B-stage sheet and a sheet-like cured epoxy resin were prepared in the same manner as in Example 1. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 7 In Example 1, boron nitride particles 3 (Mitsui Chemicals Co., Ltd., trade name “MBN-250”) and ⁇ -alumina particles (Sumitomo Chemical Co., Ltd., trade name “AA04”) were added and cured epoxy.
  • the content of boron nitride particles 1 in the resin (cured epoxy resin) is 50% by mass
  • the content of boron nitride particles 3 is 10% by mass
  • the content of ⁇ -alumina particles is 10% by mass.
  • the epoxy resin composition of Example 7 was obtained by the method similar to Example 1 except having prepared the epoxy resin composition.
  • Example 1 Using the resulting epoxy resin composition, a B-stage sheet and a sheet-like cured epoxy resin were prepared in the same manner as in Example 1. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 1 (Comparative Example 1) In Example 1, instead of boron nitride particles 1, boron nitride particles 3 (Mitsui Chemicals, Inc., trade name “MBN-250”) were used as in Example 1, except that B stage sheets and sheets were used. A cured epoxy resin was prepared. Furthermore, as in Example 1, the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1 and FIG.
  • Example 1 the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • Example 2 the length of one period of the periodic structure, the half width of the peak derived from the periodic structure in X-ray diffraction, the half width of the peak derived from the (004) plane of the boron nitride particles, and the heat The conductivity was determined. The results are shown in Table 1.
  • FIG. 1 shows an X-ray diffraction (XRD) spectrum of the cured epoxy resin of Example 1
  • FIG. 2 shows an XRD spectrum of the cured epoxy resin of Comparative Example 1.
  • the vertical axis represents diffraction intensity (CPS)
  • the horizontal axis represents diffraction angle (2 ⁇ ).
  • CPS diffraction intensity
  • the horizontal axis represents diffraction angle (2 ⁇ ).
  • the half width of the peak derived from the (004) plane of the boron nitride (BN) particles is narrow, and the peak derived from the 2 nm to 3 nm periodic structure of the epoxy resin is detected.
  • FIG. 1 shows an X-ray diffraction (XRD) spectrum of the cured epoxy resin of Example 1
  • the vertical axis represents diffraction intensity (CPS)
  • the horizontal axis represents diffraction angle (2 ⁇ ).
  • the half width of the peak derived from the (004) plane of the boron nitride (BN) particles is wide, and no peak derived from the 2 nm to 3 nm periodic structure of the epoxy resin is detected. From this, it is considered that the higher the crystallinity of the boron nitride particles, the more the cyclic structure formation of the epoxy resin is affected, and as a result, the thermal conductivity is improved.

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Abstract

La présente invention concerne une composition de résine époxy contenant des particules de nitrure de bore, la demi-largeur 2θ d'un pic de provenant du plan (004) en diffraction des rayons X (XRD) étant de 0,5 degré ou moins, un agent de durcissement et un monomère époxy à cristaux liquides représenté par la formule générale (1). [Dans la formule générale (1) X représente une liaison simple ou un groupe de liaison divalent, chaque Y représente indépendamment un groupe hydrocarboné aliphatique en C1-8, un groupe alcoxy aliphatique C1-8, un atome de fluor, un atome de chlore, un atome de brome, un atome d'iode, un groupe cyano, un groupe nitro, ou un groupe acétyle, et chaque n représente indépendamment un nombre entier de 0 à 4.]
PCT/JP2016/051144 2016-01-15 2016-01-15 Composition de résine époxy, précurseur de matériau thermoconducteur, feuille au stade b, préimprégné, matériau de dissipation de chaleur, plaque stratifiée, substrat métallique, et carte de circuit imprimé Ceased WO2017122350A1 (fr)

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JP2017561488A JPWO2017122350A1 (ja) 2016-01-15 2016-01-15 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
PCT/JP2016/051144 WO2017122350A1 (fr) 2016-01-15 2016-01-15 Composition de résine époxy, précurseur de matériau thermoconducteur, feuille au stade b, préimprégné, matériau de dissipation de chaleur, plaque stratifiée, substrat métallique, et carte de circuit imprimé

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WO2020194867A1 (fr) * 2019-03-27 2020-10-01 富士フイルム株式会社 Précurseur de feuille de dissipation thermique et procédé de production d'une feuille de dissipation thermique
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WO2019031178A1 (fr) * 2017-08-08 2019-02-14 三菱瓦斯化学株式会社 Composition de résine, produit durci, feuille de résine monocouche, feuille de résine stratifiée, préimprégné, feuille stratifiée recouverte de métal, carte de circuit imprimé, matériau d'étanchéité, matériau composite renforcé par des fibres et agent adhésif
JPWO2019031178A1 (ja) * 2017-08-08 2020-07-02 三菱瓦斯化学株式会社 樹脂組成物、硬化物、単層樹脂シート、積層樹脂シート、プリプレグ、金属箔張積層板、プリント配線板、封止用材料、繊維強化複合材料及び接着剤
JP7052797B2 (ja) 2017-08-08 2022-04-12 三菱瓦斯化学株式会社 樹脂組成物、硬化物、単層樹脂シート、積層樹脂シート、プリプレグ、金属箔張積層板、プリント配線板、封止用材料、繊維強化複合材料及び接着剤
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WO2020194867A1 (fr) * 2019-03-27 2020-10-01 富士フイルム株式会社 Précurseur de feuille de dissipation thermique et procédé de production d'une feuille de dissipation thermique
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CN115605993A (zh) * 2020-05-14 2023-01-13 昭和电工材料株式会社（Jp） 底漆、带底漆层的基板、带底漆层的基板的制造方法、半导体装置及半导体装置的制造方法
US20230183415A1 (en) * 2020-05-14 2023-06-15 Showa Denko Materials Co., Ltd. Primer, substrate equipped with primer layer, method for producing substrate equipped with primer layer, semiconductor device, and method for producing semiconductor device
WO2024204673A1 (fr) * 2023-03-31 2024-10-03 積水化学工業株式会社 Feuille de résine, élément de dissipation de chaleur, stratifié, composition de résine, article durci, carte de circuit imprimé et boîtier de puce semi-conductrice

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