WO2013065758A1 - 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置 - Google Patents

樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置 Download PDF

Info

Publication number
WO2013065758A1
WO2013065758A1 PCT/JP2012/078222 JP2012078222W WO2013065758A1 WO 2013065758 A1 WO2013065758 A1 WO 2013065758A1 JP 2012078222 W JP2012078222 W JP 2012078222W WO 2013065758 A1 WO2013065758 A1 WO 2013065758A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
filler
resin
group
cured
Prior art date
Application number
PCT/JP2012/078222
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
優香 吉田
竹澤　由高
靖夫 宮崎
高橋　裕之
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 KR1020147013363A priority Critical patent/KR101958506B1/ko
Priority to JP2013541828A priority patent/JP6102744B2/ja
Priority to CN201280053424.3A priority patent/CN104024332A/zh
Publication of WO2013065758A1 publication Critical patent/WO2013065758A1/ja

Links

Images

Classifications

    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • 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
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

  • the present invention relates to a resin composition, and a resin sheet, a prepreg, a laminate, a metal substrate, a printed wiring board, and a power semiconductor device using the resin composition.
  • a cured resin material made of a 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 method for achieving high thermal conductivity of a cured resin product there is a method of filling a resin composition with a thermal conductive filler made of a high thermal conductive ceramic to form a composite material.
  • a thermal conductive filler made of a high thermal conductive ceramic to form a composite material.
  • high thermal conductive ceramics boron nitride, alumina, aluminum nitride, silica, silicon nitride, magnesium oxide, silicon carbide and the like are known.
  • Japanese Patent Application Laid-Open No. 2009-13227 discloses that electrical insulation and thermal conductivity are good by adding a small amount of nanoparticle-sized inorganic filler in addition to the microparticle-sized thermal conductive filler. It has been reported that a resin composition for an electrically insulating material was obtained.
  • a fiber base material such as a woven fabric or a non-woven fabric is used for the purpose of improving dimensional stability, mechanical strength, etc.
  • the resin composition is used for the fiber base material.
  • a prepreg may be produced by impregnating an object.
  • the impregnation method of the fiber base material of the resin composition includes a vertical coating method in which the fiber base material is pulled through the resin composition, and the fiber base material is pressed after the resin composition is applied onto the support film.
  • There is a horizontal coating method to impregnate In the case of using the resin composition containing the filler as described above, a horizontal coating method is often applied in consideration of sedimentation of the filler, in which variation in composition is less likely to occur in the fiber base material.
  • the resin composition filled with the above-mentioned heat conductive filler having a microparticle size it is necessary to increase the filling amount of the filler in order to realize the high thermal conductivity that has been required in recent years.
  • the viscosity increases remarkably due to the interaction between the filler surface and the resin, which may easily enclose air bubbles by entraining air.
  • fluidity may be significantly reduced.
  • the resin composition highly filled with the filler is difficult to eliminate voids due to poor embedding of the surface structure of the adherend and air bubbles generated during coating. It tends to cause dielectric breakdown due to pores / bubbles.
  • a prepreg when a prepreg is produced by impregnating a fiber base material with a resin composition, if the amount of filler in the resin composition is large, the filler fits into the fiber and clogs, and the resin is sufficiently stained from the surface of the fiber base material. It may not come out or may not fill the gap between the fibers and leave holes. Furthermore, when the resin bleeds from the surface of the fiber substrate is insufficient, the adhesive strength of the prepreg to the adherend may be insufficient, causing interfacial peeling. Furthermore, the pores in the adherend interface and the fiber substrate may cause a decrease in insulation.
  • the fluidity of the resin composition is improved only by the surface treatment of the filler and the addition of a dispersant
  • the filler coverage of the surface treatment and the addition of a dispersant are added so that the resin can be sufficiently oozed out from the surface of the fiber substrate.
  • the amount is increased, chemical bonding between the filler and the resin is inhibited, and there is a problem that the thermal conductivity as the composite material is lowered.
  • the monomers having mesogenic groups are generally easy to crystallize and are solid at room temperature, so compared with general-purpose resins. May be difficult to handle. Further, when the filler is highly filled, the above-described difficulty is added, and thus molding may become more difficult.
  • an object of the present invention is to provide a resin composition that can achieve both excellent thermal conductivity and excellent fluidity.
  • Another object of the present invention is to provide a resin sheet, a prepreg, a laminate, a metal substrate, a printed wiring board, and a power semiconductor device that are configured using the resin composition and have excellent thermal conductivity and excellent insulation. .
  • the present invention includes the following aspects.
  • a particle having a peak in a range of 1 nm to less than 500 nm in a particle size distribution measured using a laser diffraction method and particles measured using a laser diffraction method A resin composition comprising a second filler having a peak in the range of 1 ⁇ m to 100 ⁇ m in diameter distribution and a thermosetting resin having a mesogenic group in the molecule.
  • the average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution is 1 nm or more and less than 500 nm, the first filler containing ⁇ -alumina, and the weight cumulative particle size distribution
  • a resin composition comprising a second filler having an average particle diameter (D50) corresponding to a cumulative 50% from the small particle diameter side of 1 ⁇ m to 100 ⁇ m, and a thermosetting resin having a mesogenic group in the molecule.
  • nitride filler includes at least one selected from the group consisting of boron nitride and aluminum nitride.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the second filler is 55% to 85% by volume in the entire volume.
  • thermosetting resin is an epoxy resin
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the mesogenic group has a structure in which three or more six-membered ring groups are connected in a straight chain.
  • the epoxy resin is the resin composition according to ⁇ 7>, which is represented by the following general formula (III) or (IV).
  • Ar 1 , Ar 2 , and Ar 3 are the same or different and represent any divalent group represented by any of the following general formulas.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
  • Q 1 and Q 2 are the same or different and each represents a linear alkylene group having 1 to 9 carbon atoms, and the methylene group constituting the linear alkylene group is substituted with an alkylene group having 1 to 18 carbon atoms
  • —O— or —N (R 7 ) — may be inserted between the methylene groups.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
  • R independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a represents an integer of 1 to 8, b, e, and g represent an integer of 1 to 6; 7 represents an integer, d and h represent an integer of 1 to 4, and f represents an integer of 1 to 5, respectively.
  • all Rs may represent the same group or different groups.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the phenol novolac resin includes a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (I-1) and (I-2) It is a resin composition.
  • R 1 independently represents an alkyl group, an aryl group, or an aralkyl group.
  • R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
  • Each m independently represents an integer of 0 to 2
  • each n independently represents an integer of 1 to 7.
  • the phenol novolak resin is the resin composition according to ⁇ 10> or ⁇ 11>, wherein a content ratio of a monomer composed of a phenol compound constituting the phenol novolak resin is 5% by mass to 80% by mass. .
  • a semi-cured resin composition which is a semi-cured product of the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • a cured resin composition that is a cured product of the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • a resin sheet which is a sheet-like molded body of the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • Adhering material the resin composition according to any one of ⁇ 1> to ⁇ 12>, and the resin sheet according to ⁇ 15> or ⁇ 16>, disposed on the adhering material And a laminate having at least one semi-cured resin composition layer selected from the group consisting of the prepregs described in ⁇ 17> or a cured resin composition layer that is a cured body.
  • Metal foil the resin composition according to any one of ⁇ 1> to ⁇ 12>, the resin sheet according to ⁇ 15> or ⁇ 16>, and the prepreg according to ⁇ 17>
  • a cured resin composition layer that is at least one cured body selected from the above and a metal plate are laminated metal substrates in this order.
  • a metal plate A metal plate, the resin composition according to any one of ⁇ 1> to ⁇ 12>, the resin sheet according to ⁇ 15> or ⁇ 16>, and the prepreg according to ⁇ 17>.
  • a printed wiring board in which a cured resin composition layer that is at least one cured body selected from the above and a wiring layer are laminated in this order.
  • a power semiconductor device comprising: a cured body of the resin sheet according to 1.
  • a resin composition that can achieve both excellent thermal conductivity and excellent fluidity.
  • a resin sheet, a prepreg, a laminate, a metal substrate, and a printed wiring board that are configured using the resin composition and have excellent thermal conductivity and excellent insulation 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 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.
  • the resin composition of the present invention has a first filler containing ⁇ -alumina having a peak in a range of 1 nm to less than 500 nm in a particle size distribution measured using a laser diffraction method, and a laser diffraction method. And a second filler having a peak in the range of 1 ⁇ m to 100 ⁇ m in the particle size distribution measured in this way, and a thermosetting resin having a mesogenic group in the molecule.
  • the resin composition has, for example, a first filler having an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution of 1 nm or more and less than 500 nm, and containing ⁇ -alumina, A second filler having an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution is mixed with a thermosetting resin having a mesogenic group in the molecule. It can produce by doing.
  • D50 average particle size
  • the resin composition of the present invention has an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution of 1 nm or more and less than 500 nm, and the first filler containing ⁇ -alumina A second filler having an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution, 1 ⁇ m to 100 ⁇ m, a thermosetting resin having a mesogenic group in the molecule, including.
  • the resin composition further includes other components as necessary. With this configuration, both excellent thermal conductivity and excellent fluidity can be achieved.
  • thermosetting resin having a mesogenic group in the molecule and a first filler having a specific average particle size including ⁇ -alumina By using a thermosetting resin having a mesogenic group in the molecule and a first filler having a specific average particle size including ⁇ -alumina, the thermal conductivity of the cured resin composition is dramatically improved. . It is described in Japanese Patent No. 4118691 that a cured product of a thermosetting resin having a mesogenic group in the molecule is excellent in thermal conductivity. However, when the thermosetting resin is used in combination with an ⁇ -alumina filler having a specific average particle size, the thermal conductivity of the cured resin composition is improved beyond the expectation described in Japanese Patent No. 4118691. This can be considered, for example, to be due to the formation of a high-order structure of a thermosetting resin having high ordering on the surface of the ⁇ -alumina filler, which is a nanoparticle.
  • the thermal conductivity of the cured resin composition is greatly improved.
  • curing is achieved by combining a second filler having an average particle size (D50) of 1 ⁇ m to 100 ⁇ m and a first filler having an average particle size (D50) containing ⁇ -alumina of 1 nm or more and less than 500 nm.
  • D50 average particle size
  • the thermal conductivity of the resin composition is greatly improved.
  • the present inventors consider as follows. However, the present invention is not limited to the following estimation mechanism.
  • the resin exists at the interface between the fillers. Since the resin has a lower thermal conductivity than the filler, it becomes difficult for heat to be transferred between the fillers. Therefore, no matter how high the filler is filled and the fillers are brought into close contact with each other, heat conduction is largely lost at the filler interface.
  • the thermosetting resin having mesogenic groups in the molecules existing between the fillers efficiently transfers heat, and further the thermosetting having mesogenic groups in the first filler and molecules.
  • the thermal conductivity between the first filler and between the first filler and the second filler is further improved, so there is less loss of heat conduction at the filler interface, resulting in a cured resin composition. It is thought that the thermal conductivity of the is improved. This estimation mechanism will be further described with reference to the drawings.
  • FIG. 1 is a cross-sectional view conceptually showing the cured resin composition according to this embodiment, and arrows in FIG. 1 schematically show heat conduction paths.
  • the first filler 20 has a smaller average particle diameter than the second filler 10, and thus can enter a gap formed between the second fillers 10 in the cured resin composition. it can.
  • a cured product 30 made of a thermosetting resin having a mesogenic group forms a higher order structure as shown in the enlarged view of FIG.
  • cured material 30 was formed in the surface comprises the new heat conduction path
  • a cured product 30 made of a thermosetting resin having a mesogenic group forms a higher order structure on the surface of the first filler 20.
  • the higher-order structure formation part (denoted as 30a) capable of efficiently transferring heat exists around the first filler 20.
  • the first filler 20 having the higher-order structure forming portion 30a enters so as to fill a gap formed between the second fillers 10 for the reason described above. It is considered that heat can be transferred very efficiently and higher thermal conductivity can be obtained.
  • the arrows in FIG. 3 schematically show the heat conduction paths as in FIG. For example, heat conduction is performed in the order of the second filler 10, the higher-order structure forming part (30 a) by the cured product 30, the first filler 20, the higher-order structure forming part 30 a by the cured product 30, and the second filler 10. Heat can be transferred without loss.
  • FIG.4 and FIG.5 shows about an example of a structure of the cured resin composition different from this embodiment.
  • FIG. 4 schematically shows a case where the cured resin composition does not contain the first filler 20. In this case, since the gap formed between the second fillers 10 inhibits heat conduction, it is considered that high heat conductivity cannot be obtained.
  • FIG. 5 schematically shows a case where the cured resin composition contains a filler not corresponding to the first filler 20 (for example, a filler 40 having an average particle diameter (D50) made of a substance other than ⁇ -alumina of 1 nm or more and less than 500 nm). Show.
  • D50 average particle diameter
  • the higher order structure of the cured product 30 is not formed on the surface of the filler 40. For this reason, the gap formed between the fillers 40 or between the second filler 20 and the filler 40 inhibits heat conduction. For this reason, it is thought that high thermal conductivity cannot be obtained.
  • FIG. 6 is a cross-sectional view conceptually showing a cured resin composition according to Comparative Example 1 described later, and the arrows in FIG. 6 schematically show the heat conduction paths as in FIG.
  • the cured resin composition composed of the second filler 10 and the cured product 30 made of the thermosetting resin having a mesogenic group as shown in FIG. It is filled with the cured resin 30 having the next structure.
  • the cured resin 30 having a higher order structure has higher thermal conductivity than a general cured resin, the first order in which the higher order structure of the cured resin 30 having a mesogenic group on the surface in FIG. 6 is formed. Compared with the filler 20, thermal conductivity is lowered. Therefore, in the cured resin composition as shown in FIG. 6, it is thought that thermal conductivity falls compared with a cured resin composition as shown in FIG.
  • FIG. 7 is a cross-sectional view conceptually showing a cured resin composition according to Comparative Examples 2 and 4 to be described later, and the arrows in FIG. 7 schematically show the heat conduction paths as in FIG. .
  • heat having an average particle diameter (D50) other than ⁇ -alumina of 1 nm or more and less than 500 nm for example, silica filler or ⁇ -alumina filler
  • second filler 10 for example, silica filler or ⁇ -alumina filler
  • mesogenic groups for example, silica filler or ⁇ -alumina filler
  • the cured resin 30 having a higher order structure.
  • the filler 40 having an average particle diameter (D50) other than ⁇ -alumina of 1 nm or more and less than 500 nm and the cured resin 30 having a higher order structure, the higher order structure of the cured resin 30 having a mesogenic group on the surface in FIG. Compared with the formed first filler 20, the thermal conductivity is lowered. Therefore, it is considered that the cured resin composition as shown in FIG. 7 has a lower thermal conductivity than the cured resin composition as shown in FIG.
  • FIG. 8 is a cross-sectional view conceptually showing a cured resin composition according to Comparative Example 5 described later, and the arrows in FIG. 8 schematically show the heat conduction paths as in FIG.
  • the second filler 10 in the cured resin composition composed of the first filler 20, the second filler 10, and a cured product 50 made of a thermosetting resin having no mesogenic group, the second filler 10
  • the gap formed between the first filler 20 and the cured resin 50 that does not form a higher order structure is filled.
  • the first filler 20 and the cured resin 50 that does not form a higher order structure are more thermally conductive than the first filler 20 in which the higher order structure of the cured resin 30 having a mesogenic group is formed on the surface in FIG. Decreases. Therefore, in the cured resin composition as shown in FIG. 8, it is thought that thermal conductivity falls compared with a cured resin composition as shown in FIG.
  • the higher order structure means a structure including a higher order structure in which 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. That is, in the observation in the crossed Nicols state, it can be distinguished by seeing interference fringes due to depolarization.
  • This higher order structure usually exists in an island shape in the cured 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.
  • thermosetting resin having a mesogenic group in the molecule as the thermosetting resin, the present inventors can form a higher order structure of a cured resin product having high order on the first filler surface. I found out. Furthermore, it has been found that the thermosetting resin having a mesogenic group exhibits higher order with the first filler as a nucleus, and the thermal conductivity of the cured resin itself is improved.
  • the first filler in which the higher-order structure of the cured resin having a mesogenic group is formed on the surface enters the gaps between the second fillers, and increases the heat conduction path. High thermal conductivity can be obtained.
  • the presence of the higher order structure of the cured resin on the first filler surface can be found as follows.
  • a cured product (thickness: 0.1 ⁇ m to 20 ⁇ m) of a thermosetting resin having a mesogenic group containing 5% by volume to 10% by volume of the first filler is used with a polarizing microscope (eg, Olympus BX51).
  • a polarizing microscope eg, Olympus BX51.
  • a region where no interference pattern is observed (that is, a region where the resin does not form a higher order structure) becomes a dark field, and cannot be distinguished from the filler portion.
  • the region where the interference pattern is not observed is not a dark field, and can be distinguished from the filler portion.
  • the above phenomenon can be observed not only with the first filler but also with a high thermal conductivity ceramic filler such as boron nitride, alumina, aluminum nitride, silica, etc. Even if (D50) is outside the range of the first filler, the area of the interference pattern formed around the filler is extremely large.
  • the resin composition contains a first filler having a specific average particle diameter (D50) and a second filler in combination.
  • the average particle diameter (D50) in the present invention means a particle diameter at which accumulation is 50% when a weight cumulative particle size distribution is drawn from the small particle diameter side.
  • the weight cumulative particle size distribution is measured using a laser diffraction method.
  • the particle size distribution measurement using the laser diffraction method can be performed using a laser diffraction scattering particle size distribution measuring apparatus (for example, LS13 manufactured by Beckman Coulter, Inc.).
  • the filler is an organic solvent dispersion
  • the filler dispersion for measurement is diluted with the same organic solvent so that the amount of light is appropriate for the sensitivity of the apparatus.
  • the filler is a powder
  • the powder is put into a 0.1% by mass sodium metaphosphate aqueous solution, ultrasonically dispersed, and measured at a concentration that provides an appropriate amount of light for the sensitivity of the apparatus.
  • a first filler having an average particle diameter (D50) of 1 nm or more and less than 500 nm By incorporating a first filler having an average particle diameter (D50) of 1 nm or more and less than 500 nm into the resin composition, lubrication between second fillers having an average particle diameter (D50) of 1 ⁇ m to 100 ⁇ m contained in the resin composition, a lubricating effect between the second filler and the fiber base material can be obtained.
  • the resin sheet and resin-coated metal foil formed using such a resin composition having excellent fluidity it is possible to satisfactorily fill the pores formed during the production and the voids with the interface of the adherend, Improves dielectric breakdown.
  • the second filler can be satisfactorily slipped in the gaps of the fiber base material, and the resin composition has a good fiber base. Since the material oozes out from the material and can fill well the inside of the base material and the interface with the adherend at the time of application, the dielectric breakdown property is improved. Furthermore, due to the good fluidity, when hot pressing is performed after coating, the resin can be oozed out to the surface of the fiber substrate, and the adhesiveness is also improved.
  • the resin composition is excellent in thermal conductivity and fluidity, a laminate, a metal substrate, and a printed wiring board having an insulating layer obtained by curing the resin composition exhibit higher thermal conductivity and insulation.
  • the hereinafter, the material used for the resin composition and the physical properties of the resin composition will be described.
  • the resin composition includes a first filler having a peak in a range of 1 nm or more and less than 500 nm in a particle size distribution measured using a laser diffraction method, and containing ⁇ -alumina. That is, the resin composition includes a first filler having an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution of 1 nm or more and less than 500 nm and containing ⁇ -alumina. Including.
  • D50 average particle size
  • the first filler preferably has a peak in the range of 1 nm to 450 nm in the particle size distribution measured using a laser diffraction method, and in the range of 50 nm to 450 nm. It preferably has a peak, more preferably has a peak in the range of 100 nm to 450 nm, more preferably has a peak in the range of 100 nm to 300 nm, and still more preferably has a peak in the range of 100 nm to 200 nm.
  • the average particle diameter (D50) of the first filler is preferably 1 nm to 450 nm, more preferably 50 nm to 450 nm, and more preferably 100 nm to 450 nm from the viewpoint of improving thermal conductivity and fluidity. More preferably, the thickness is more preferably 100 nm to 300 nm, and still more preferably 100 nm to 200 nm.
  • the average particle diameter (D50) of the first filler is 500 nm or more, the first filler cannot sufficiently enter the gap between the second filler, and as a result, the entire filler in the resin composition is filled. There is a tendency for the amount to decrease and the thermal conductivity to decrease. Moreover, if the average particle diameter (D50) of a 1st filler is less than 1 nm, the lubricity between 2nd fillers or between a 2nd filler and a fiber base material may not fully be obtained.
  • the method for obtaining the average particle size of the first filler is as described above.
  • the first filler contains ⁇ -alumina.
  • ⁇ -alumina By including ⁇ -alumina, sufficient thermal conductivity tends to be obtained.
  • ⁇ -alumina a resin composition having a high melting point, high mechanical strength, and electrical insulation can be obtained, and the filling property of the first filler is improved.
  • the shape of the ⁇ -alumina is preferably round from the viewpoint of thermal conductivity and filling properties.
  • the shape of the ⁇ -alumina can be measured with a scanning electron microscope (SEM).
  • the first filler may further contain alumina other than ⁇ -alumina.
  • alumina other than ⁇ -alumina is further included, the alumina particles other than ⁇ -alumina are preferably round.
  • the shape of the filler can be measured in the same manner as the shape of ⁇ -alumina. Examples of alumina other than ⁇ -alumina include ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina.
  • the first filler may further contain ceramics other than alumina as necessary.
  • ceramics other than alumina for example, boron nitride, aluminum nitride, silica, magnesium oxide, silicon nitride, silicon carbide and the like may be included.
  • the content of ⁇ -alumina in the first filler is preferably 80% by volume or more, more preferably 90% by volume or more of the total volume of the first filler from the viewpoint of thermal conductivity and fluidity. Preferably, the volume is 100% by volume.
  • the thermosetting resin having a mesogenic group in the molecule has a large higher-order structure forming power and tends to provide sufficient thermal conductivity.
  • the presence of ⁇ -alumina in the first filler can be confirmed by an X-ray diffraction spectrum. Specifically, for example, 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 rate of the 1st filler contained in the said resin composition is not restrict
  • the first filler is preferably contained in an amount of 0.1% by volume to 10% by volume in the total volume of the total solid content of the resin composition.
  • the lubricity between the second filler and between the second filler and the fiber substrate is further improved.
  • the effect which raises and raises the heat conductivity of a resin composition more is acquired.
  • the content of the first filler is preferably 0.2% by volume to 10% by volume, and more preferably 0.2% by volume to 8% by volume from the viewpoint of improving thermal conductivity and fluidity.
  • the total solid content of the resin composition means a residue obtained by removing volatile components from the resin composition.
  • each variable is as follows.
  • Aw Mass composition ratio (% by mass) of the first filler Bw: mass composition ratio (mass%) of the second filler Cw: mass composition ratio of thermosetting resin (mass%)
  • Dw mass composition ratio of curing agent (mass%)
  • Ew Mass composition ratio (% by mass) of other optional components (excluding organic solvents)
  • Dd Specific gravity of the curing agent
  • Ed Specific gravity of other optional components (excluding organic solvents)
  • the first filler can be used singly or in combination of two or more.
  • two or more kinds of ⁇ -alumina having an average particle size (D50) in the range of 1 nm or more and less than 500 nm and different D50s can be used in combination, but the combination is not limited thereto.
  • the first filler may have a single peak or a plurality of peaks when a particle size distribution curve having a particle diameter on the horizontal axis and a frequency on the vertical axis is drawn. Good.
  • the first filler having a plurality of peaks in the particle size distribution curve can be constituted by combining two or more first fillers having different average particle diameters (D50), for example.
  • the resin composition contains at least one second filler having a peak in the range of 1 ⁇ m to 100 ⁇ m in the particle size distribution measured using a laser diffraction method. That is, the resin composition contains at least one second filler having an average particle size (D50) determined from a weight cumulative particle size distribution of 1 ⁇ m to 100 ⁇ m.
  • D50 average particle size
  • the second filler has a higher thermal conductivity than a cured resin of a thermosetting resin, and is not particularly limited as long as the average particle diameter (D50) is 1 ⁇ m to 100 ⁇ m. It can be appropriately selected from those used as fillers.
  • the second filler is preferably electrically insulating.
  • the thermal conductivity of the second filler is not particularly limited as long as it is higher than the cured resin.
  • the thermal conductivity is preferably 1 W / mK or more, and more preferably 10 W / mK or more.
  • the second filler examples include boron nitride, aluminum nitride, alumina, silica, and magnesium oxide. From the viewpoint of further improving the thermal conductivity, a nitride filler is preferable, and among them, at least one of boron nitride and aluminum nitride is preferable.
  • the second filler can be used singly or in combination of two or more.
  • boron nitride and aluminum nitride can be used in combination, but are not limited to this combination.
  • the content of the second filler is not particularly limited, but it is preferably contained at 55 volume% to 85 volume% in the total volume of the total solid content of the resin composition.
  • the content of the second filler in the resin composition is 55% by volume or more, the thermal conductivity is more excellent. Moreover, a moldability and adhesiveness improve that it is 85 volume% or less.
  • the content of the second filler in the present invention is more preferably 60% by volume to 85% by volume in the total volume of the total solid content of the resin composition from the viewpoint of increasing the thermal conductivity, and from the viewpoint of fluidity. More preferably, it is 65 volume% to 85 volume%.
  • Second filler (Bw / Bd) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd) + (Ew / Ed))) ⁇ 100
  • each variable is as follows.
  • Aw Mass composition ratio (% by mass) of the first filler Bw: mass composition ratio (mass%) of the second filler Cw: mass composition ratio of thermosetting resin (mass%)
  • Dw Curing agent mass composition cost (mass%)
  • Ew Mass composition ratio (% by mass) of other optional components (excluding organic solvents)
  • Dd Specific gravity of the curing agent
  • Ed Specific gravity of other optional components (excluding organic solvents)
  • the second filler may have a single peak or a plurality of peaks when a particle size distribution curve having a particle diameter on the horizontal axis and a frequency on the vertical axis is drawn. Good.
  • the filling property of the second filler is improved, and the thermal conductivity as the cured resin composition is improved.
  • the second filler When the second filler has a single peak when a particle size distribution curve is drawn, it preferably has a peak in the range of 1 ⁇ m to 80 ⁇ m, more preferably has a peak in the range of 1 ⁇ m to 50 ⁇ m, It is more preferable to have a peak in the range of 1 ⁇ m to 30 ⁇ m, and it is more preferable to have a peak in the range of 1 ⁇ m to 20 ⁇ m. That is, the average particle diameter (D50) of the second filler is preferably 1 ⁇ m to 80 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and even more preferably 1 ⁇ m to 30 ⁇ m from the viewpoint of thermal conductivity. More preferably, it is 1 ⁇ m to 20 ⁇ m. Moreover, the 2nd filler which a particle size distribution curve has a some peak can be comprised combining 2 or more types of 2nd fillers which have a different average particle diameter (D50), for example.
  • D50 average particle diameter
  • the filler (A) having an average particle diameter (D50) of 10 ⁇ m or more and 100 ⁇ m or less, and the average particle It is a mixed filler with a filler (B) whose diameter (D50) is 1 ⁇ 2 or less of the filler (A) and is 1 ⁇ m or more and less than 10 ⁇ m, and the filler (A) is 60 with respect to the total volume of the second filler. It is preferable that the filler is filled at a ratio of volume% to 90 volume%, and the filler (B) is 10 volume% to 40 volume% (however, the total volume% of the fillers (A) and (B) is 100 volume%). .
  • a filler (B ′) that is 1 ⁇ 2 or less of 5 ⁇ m or more and less than 10 ⁇ m, a filler (C ′) whose average particle diameter (D50) is 1 ⁇ 2 or less of the filler (B ′) and is 1 ⁇ m or more and less than 5 ⁇ m;
  • the filler (A ′) is 30% by volume to 89% by volume, the filler (B ′) is 10% by volume to 40% by volume, and the filler (C ′ ) Is preferably 1% by volume to 30% by volume (provided that the total volume% of fillers (A ′), (B ′), and (C ′) is 100% by volume).
  • the average particle diameter (D50) of the fillers (A) and (A ′) is a cured resin composition in a target resin sheet or laminate when the resin composition is applied to a resin sheet or laminate described later.
  • D50 average particle diameter of the fillers (A) and (A ′)
  • 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 fillers (A) and (A ′) are preferably boron nitride or aluminum nitride, but the fillers (B) and (B ′) and the filler (C ′) need not necessarily be boron nitride or aluminum nitride. There is no. For example, alumina may be used.
  • the average particle diameter (D50) is 1 ⁇ m to 100 ⁇ m in the entire second filler.
  • the resin composition may further contain a third filler having an average particle diameter (D50) of 1 nm or more and less than 500 nm and 1 ⁇ m to 100 ⁇ m as necessary, and having thermal conductivity. Even when a third filler having an average particle diameter (D50) of 1 nm to less than 500 nm and outside the range of 1 ⁇ m to 100 ⁇ m is used in combination, the second filler having an average particle diameter (D50) of 1 ⁇ m to 100 ⁇ m is a resin. It is preferably contained at 55 volume% to 85 volume% in the total volume of the composition.
  • the average particle diameter (D50) of the third filler is preferably 500 nm or more and less than 1 ⁇ m, and more preferably 500 nm or more and 800 nm or less.
  • the content rate of the 3rd filler in the case where the said resin composition contains a 3rd filler is not restrict
  • the total volume of the resin composition is preferably 1% by volume to 40% by volume, and more preferably 1% by volume to 20% by volume.
  • the preferable aspect of the heat conductivity of a 3rd filler is the same as that of said 2nd filler.
  • the ratio of the average particle diameter (D50) of the second filler to the average particle diameter (D50) of the first filler contained in the resin composition (second filler / first filler) is not particularly limited. From the viewpoint of thermal conductivity and fluidity, it is preferably 10 to 500, more preferably 30 to 300. When the particle size distribution curve of the second filler has a plurality of peaks, the ratio of the particle diameter corresponding to the peak having the maximum particle diameter to the average particle diameter (D50) of the first filler is 10 to 500. Is more preferable, 30 to 300 is more preferable, and 100 to 300 is more preferable.
  • the ratio (second filler / first filler) of the second filler content (volume%) to the first filler content (volume%) contained in the resin composition is not particularly limited. From the viewpoint of thermal conductivity and fluidity, it is preferably 5 to 500, more preferably 5 to 350.
  • thermosetting resin The resin composition contains at least one thermosetting resin having a mesogenic group in the molecule.
  • the mesogenic group refers to a functional group that facilitates the expression of crystallinity and 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.
  • thermosetting resin in the present invention is not particularly limited as long as it is a compound having at least one mesogenic group and at least two thermosetting functional groups in the molecule.
  • Specific examples include epoxy resins, polyimide resins, polyamideimide resins, triazine resins, phenol resins, melamine resins, polyester resins, cyanate ester resins, and modified resins of these resins. These resins may be used alone or in combination of two or more.
  • the thermosetting resin is preferably at least one resin selected from an epoxy resin, a phenol resin, and a triazine resin from the viewpoint of heat resistance, and more preferably an epoxy resin from the viewpoint of adhesiveness.
  • the said epoxy resin may be used individually by 1 type, or may use 2 or more types together.
  • mesogen-containing epoxy resin For the specific content of the epoxy resin having a mesogenic group in the molecule (hereinafter also referred to as “mesogen-containing epoxy resin”), reference can be made to, for example, the description of Japanese Patent No. 4118691.
  • thermosetting resin in this invention is not limited to these.
  • mesogen-containing epoxy resin examples include an epoxy resin represented by the following general formula (II) (described in Japanese Patent No. 4118691), an epoxy resin represented by the following general formula (III) (Japanese Patent No. 4619770, JP 2008) No. 13759), an epoxy resin represented by the following general formula (IV) (described in JP-A-2011-74366), an epoxy resin represented by the following general formula (V) (JP-A 2010-241797) And an epoxy resin represented by the following chemical formula (VI) (described in JP-A-2011-98952), and the like.
  • general formula (II) described in Japanese Patent No. 4118691
  • an epoxy resin represented by the following general formula (III) Japanese Patent No. 4619770, JP 2008) No. 13759
  • an epoxy resin represented by the following general formula (IV) described in JP-A-2011-74366
  • an epoxy resin represented by the following general formula (V) JP-A 2010-241797)
  • n 4, 6 or 8.
  • Ar 1 , Ar 2 , and Ar 3 are the same or different and each represents any divalent group represented by any of the following general formulas.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
  • Q 1 and Q 2 are the same or different and each represents a linear alkylene group having 1 to 9 carbon atoms, and the methylene group constituting the linear alkylene group is substituted with an alkylene group having 1 to 18 carbon atoms
  • —O— or —N (R 7 ) — may be inserted between the methylene groups.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
  • each R independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
  • a is an integer of 1 to 8
  • b is an integer of 1 to 8
  • e is integers of 1 to 6
  • c is 1 to 7
  • h are integers of 1 to 4
  • f is an integer of 1 to 5, respectively.
  • all Rs may represent the same group or different groups.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • each R 1 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
  • R 2 each independently represents a hydrogen atom, or 1 to 3 carbon atoms.
  • R 3 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
  • R 4 each independently represents R 5 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
  • R 5 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
  • 6 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
  • R 7 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms
  • R 8 represents a hydrogen atom.
  • Methyl group or C 1-3 It represents a Kokishi group.
  • YL6121H (made by Mitsubishi Chemical Corporation) etc. are mentioned as a commercial item.
  • the mesogen-containing epoxy resin is preferably an epoxy resin having a structure in which three or more six-membered ring groups are connected in a straight chain in a mesogen group. Such a resin can easily form a higher-order structure, and higher thermal conductivity can be obtained.
  • the number of linearly linked 6-membered cyclic groups contained in the mesogenic group is preferably 3 or more, but more preferably 3 or 4 from the viewpoint of moldability.
  • the 6-membered cyclic group connected in a straight chain contained in the mesogenic group is a cyclohexane, even if it is a 6-membered cyclic group derived from an aromatic ring represented by acenes such as benzene, pyridine, toluene, or naphthalene. , Cyclohexene, piperidine and other aliphatic rings derived from an aliphatic ring. Among them, at least one is preferably a 6-membered ring group derived from an aromatic ring, and one of the 6-membered ring groups connected in a straight chain contained in the mesogen group is an aliphatic ring, and the remaining More preferably, the rings are all aromatic rings.
  • the epoxy resins having a structure in which three or more 6-membered rings are linearly linked in the mesogenic group correspond to the above general formulas (II) to (VI).
  • general formula (III) or general formula (VI) from a heat conductive viewpoint is preferable.
  • epoxy resins represented by the following formulas (VII), (VIII), (IX), and (X) are preferable for the resin composition because they have excellent fluidity and adhesiveness in addition to thermal conductivity. Can be applied.
  • thermosetting resin may be a monomer or a prepolymer obtained by partially reacting the monomer with a curing agent or the like.
  • Resins having mesogenic groups in the molecule are generally easy to crystallize and have low solubility in solvents, but can be partially reacted and polymerized to suppress crystallization, thus improving moldability There is.
  • thermosetting resin is preferably contained in an amount of 10 to 40% by volume of the total volume of the total solid content of the resin composition from the viewpoints of moldability, adhesiveness, and thermal conductivity, and 15 volume. More preferably, it is contained in an amount of from 35% to 35% by volume, and more preferably from 15% to 30% by volume.
  • curing agents and hardening accelerator shall be included in the content rate of a thermosetting resin here.
  • thermosetting resin / first filler The ratio (thermosetting resin / first filler) of the thermosetting resin content (volume%) to the first filler content (volume%) contained in the resin composition is not particularly limited. From the viewpoint of thermal conductivity and fluidity, it is preferably 1 to 200, more preferably 2.5 to 150.
  • the epoxy resin monomer represented by the general formula (III) or the general formula (IV) forms a higher order structure having higher ordering with ⁇ -alumina contained in the first filler as a center.
  • the thermal conductivity after curing tends to improve dramatically. This is thought to be due to the presence of ⁇ -alumina, the epoxy resin having a higher order structure forms an efficient heat conduction path, and high heat conductivity can be obtained.
  • D50 of ⁇ -alumina contained in the resin composition is 1 nm or more and less than 500 nm, the effect of forming a higher-order structure of the epoxy resin monomer tends to be remarkable, and the improvement of thermal conductivity tends to be remarkable. It is in.
  • the epoxy resin monomer represented by the general formula (III) or the general formula (IV) has a high transition temperature to the liquid crystal phase, that is, a melting temperature as high as 150 ° C. Therefore, when the epoxy resin monomer is melted, although depending on the curing agent and curing catalyst used, the curing reaction usually proceeds simultaneously with melting. As a result, the epoxy resin monomer becomes a cured body before forming a higher order structure. However, in a system containing ⁇ -alumina having D50 of 1 nm or more and less than 500 nm, 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 (III) or the general formula (IV) can only exhibit a nematic structure as a single resin. 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 (III) or the general formula (IV) exhibits a smectic structure having higher order than the nematic structure. . As a result, it exhibits a high thermal conductivity that cannot be predicted from a cured body made of a single resin.
  • 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.
  • a cured product of a composition in which 5 to 10% by volume of ⁇ -alumina having a different D50 in the epoxy resin monomer represented by the general formula (III) or (IV) is contained is observed with a polarizing microscope by the method described above. Then, in the case of ⁇ -alumina having D50 of 1 nm or more and less than 500 nm, the area of the region showing the interference pattern becomes the largest. From this, the effect of forming the higher order structure of the epoxy resin monomer represented by the general formula (III) or the general formula (IV) when ⁇ -alumina having a D50 of 1 nm or more and less than 500 nm is used is very remarkable. It can be judged.
  • Ar 1 , Ar 2 , and Ar 3 are preferably the same or different and each is preferably a divalent group (1), (3), or (8) represented by the following general formula: More preferably, 1 and Ar 3 are (8) and Ar 2 is (3).
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different, and are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • Q 1 and Q 2 are the same or different and are each preferably a linear alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.
  • R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and a hydrogen atom. More preferably. 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 one 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 resin composition preferably includes at least one curing agent.
  • the curing agent is not particularly limited as long as the thermosetting resin can be thermoset.
  • Examples of the curing agent when the thermosetting resin is an epoxy resin include polyaddition curing agents such as acid anhydride curing agents, amine curing agents, phenol curing agents, and mercaptan curing agents, and imidazole. And the like, and the like.
  • polyaddition curing agents such as acid anhydride curing agents, amine curing agents, phenol curing agents, and mercaptan curing agents, and imidazole. And the like, and the like.
  • it is preferable to use at least one selected from amine-based curing agents and phenol-based curing agents and from the viewpoint of storage stability, it is preferable to use at least one phenol-based curing agent. More preferred.
  • amine curing agent those usually used can be used without particular limitation, and those commercially available may be used.
  • a polyfunctional curing agent having two or more functional groups is preferable from the viewpoint of curability, and a polyfunctional curing agent having a rigid skeleton is more preferable from the viewpoint of thermal conductivity.
  • bifunctional amine curing agents examples include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino-3,3′-dimethoxybiphenyl 4,4′-diaminophenylbenzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 1,8-diaminonaphthalene and the like.
  • At least one selected from 4,4′-diaminodiphenylmethane and 1,5-diaminonaphthalene is preferable, and 1,5-diaminonaphthalene is more preferable.
  • phenolic curing agent those usually used can be used without particular limitation, and commercially available low molecular phenolic compounds and phenol resins obtained by novolacizing them can be used.
  • low molecular weight phenol compounds examples include monofunctional compounds such as phenol, o-cresol, m-cresol, and p-cresol, bifunctional compounds such as catechol, resorcinol, and hydroquinone, and 1,2,3-triol. Trifunctional compounds such as hydroxybenzene, 1,2,4-trihydroxybenzene, 1,3,5-trihydroxybenzene and the like can be used.
  • a phenol novolac resin obtained by connecting these low molecular phenol compounds with a methylene chain to form a novolak can also be used as a curing agent.
  • the phenolic curing agent is preferably a bifunctional phenolic compound such as catechol, resorcinol, hydroquinone, or the like, or a phenol novolac resin in which these are connected by a methylene chain, and from the viewpoint of heat resistance.
  • a phenol novolak resin in which these low-molecular bifunctional phenolic compounds are linked by a methylene chain is more preferable.
  • the phenol novolak resin include a resin obtained by novolakizing one phenol compound such as a cresol novolak resin, a catechol novolak resin, a resorcinol novolak resin, and a hydroquinone novolak resin, a catechol resorcinol novolak resin, and a resorcinol hydroquinone novolak resin.
  • a resin in which two or more phenol compounds are novolakized can be exemplified.
  • the phenol novolac resin is preferably a phenol novolac resin containing a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (I-1) and (I-2). .
  • each R 1 independently represents an alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group, and aralkyl group represented by R 1 may further have a substituent, if possible.
  • the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroxyl group.
  • m independently represents an integer of 0 to 2, and when m is 2, two R 1 s may be the same or different. In the present invention, each m is preferably independently 0 or 1, more preferably 0. Each n independently represents an integer of 1 to 7.
  • R 2 and R 3 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 2 and R 3 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 2 and R 3 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, and are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom.
  • An aryl group of 6 to 12 is preferable, and a hydrogen atom is more preferable.
  • at least one of R 2 and R 3 is preferably an aryl group, 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 according to the present invention may contain one type of compound having the structural unit represented by the general formula (I-1) or (I-2) alone, or may contain two or more types. There may be. Preferably, it includes at least a compound having a structural unit derived from resorcinol represented by the general formula (I-1).
  • the compound having the structural unit represented by the general formula (I-1) may further include at least one partial structure derived from a phenol compound other than resorcinol.
  • the phenol compound other than resorcinol in the general formula (I-1) include phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,3 , 5-trihydroxybenzene and the like.
  • the partial structure derived from these may be included individually by 1 type or in combination of 2 or more types.
  • the compound having a structural unit derived from catechol represented by the general formula (I-2) 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 benzene 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, hydroquinone, 1,2,3-trihydroxybenzene, from the viewpoint of thermal conductivity, adhesiveness, and storage stability. It is preferably a partial structure derived from at least one selected from 1,2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene, and a portion derived from at least one selected from catechol and hydroquinone A structure is more preferable.
  • the content ratio of the partial structure derived from resorcinol is not particularly limited. From the viewpoint of 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 formula (I-1) is preferably 55% by mass or more. Furthermore, from the viewpoint of glass transition temperature (Tg) and linear expansion coefficient, it is more preferably 60% by mass or more, further preferably 80% by mass or more, and from the viewpoint of thermal conductivity, 90% by mass or more. More preferably it is.
  • Tg glass transition temperature
  • linear expansion coefficient it is more preferably 60% by mass or more, further preferably 80% by mass or more, and from the viewpoint of thermal conductivity, 90% by mass or more. More preferably it is.
  • the phenol novolac resin is more preferably a phenol novolak resin containing a compound having a partial structure represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4): preferable.
  • the phenol novolac resin is a phenol volac resin containing a compound having a partial structure represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4): Is more preferable.
  • n are each independently a positive number, and indicate the number of repetitions of each repeating unit.
  • Ar represents a group represented by any one of the following general formulas (II-a) and (II-b).
  • R 11 and R 14 each independently represents a hydrogen atom or a hydroxyl group.
  • R 12 and R 13 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the curing agent having a partial structure represented by at least one of the above general formulas (II-1) to (II-4) is produced as a by-product by a production method described later in which a bifunctional phenol compound is novolakized. It is possible.
  • the partial structures represented by the general formulas (II-1) to (II-4) may be included as the main chain skeleton of the curing agent or may be included as a part of the side chain. Further, each repeating unit constituting the partial structure represented by any one of the general formulas (II-1) to (II-4) may be included randomly or regularly. It may be included or may be included in a block shape.
  • the hydroxyl substitution position is not particularly limited as long as it is on the aromatic ring.
  • a plurality of Ar may all be the same atomic group or may contain two or more kinds of atomic groups.
  • Ar represents a group represented by any one of the general formulas (II-a) and (II-b).
  • R 11 and R 14 in the general formulas (II-a) and (II-b) are each independently a hydrogen atom or a hydroxyl group, but are preferably a hydroxyl group from the viewpoint of thermal conductivity. Further, the substitution positions of R 11 and R 14 are not particularly limited.
  • R 12 and R 13 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 12 and R 13 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl Group, and octyl group.
  • substitution positions of R 12 and R 13 in the general formulas (II-a) and (II-b) are not particularly limited.
  • Ar in the above general formulas (II-a) and (II-b) is a group derived from dihydroxybenzene (from the above general formula (II-a), from the viewpoint of achieving the effects of the present invention, particularly excellent thermal conductivity.
  • a group derived from dihydroxynaphthalene a group in which R 14 is a hydroxyl group in the above general formula II-b), and at least R 11 is a hydroxyl group and R 12 and R 13 are hydrogen atoms
  • One type is preferable.
  • 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 is more preferably a group derived from dihydroxybenzene, and a group derived from 1,2-dihydroxybenzene (catechol) and 1, More preferably, it is at least one selected from the group consisting of groups derived from 3-dihydroxybenzene (resorcinol). Furthermore, it is preferable that at least a group derived from resorcinol is included as Ar from the viewpoint of particularly improving thermal conductivity. Further, from the viewpoint of particularly improving the thermal conductivity, the structural unit represented by the repeating number n preferably contains a group derived from resorcinol.
  • the content of the structural unit containing a group derived from resorcinol is 55% by mass or more in the total mass of the compound having a partial structure represented by at least one of general formulas (II-1) to (II-4) It is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • Phenol novolac resins having a partial structure represented by at least one of the general formulas (II-1) to (II-4) are particularly those in which Ar is substituted or unsubstituted dihydroxybenzene and substituted or unsubstituted dihydroxynaphthalene.
  • Ar is substituted or unsubstituted dihydroxybenzene and substituted or unsubstituted dihydroxynaphthalene.
  • the synthesis is easy and a curing agent having a low softening point tends to be obtained. Therefore, there are advantages such as easy manufacture and handling of a resin composition containing such a resin.
  • the phenol novolak resin having a partial structure represented by any one of the above general formulas (II-1) to (II-4) is obtained as a fragment component thereof by the field desorption ionization mass spectrometry (FD-MS).
  • FD-MS field desorption ionization mass spectrometry
  • the molecular weight of the phenol novolac resin having a partial structure represented by any one of the general formulas (II-1) to (II-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 equivalent of the phenol novolac resin having a partial structure represented by any one of the general formulas (II-1) to (II-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 in average, more preferably 50 to 120, and even more preferably 55 to 120.
  • the phenol novolac resin may contain a monomer that is a phenol compound constituting the phenol novolac resin.
  • a monomer that is a phenol compound constituting the phenol novolac resin There is no particular limitation on the content ratio of the monomer that is a phenol compound constituting the phenol novolac resin (hereinafter also referred to as “monomer content ratio”). From the viewpoint of thermal conductivity, heat resistance, and moldability, it 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.
  • 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 resin composition is not particularly limited.
  • the curing agent is an amine curing agent
  • the ratio of the active hydrogen equivalent of the amine curing agent (amine equivalent) to the epoxy equivalent of the mesogen-containing epoxy resin (amine equivalent / epoxy equivalent) is 0.5 to 2 is preferable, and 0.8 to 1.2 is more preferable.
  • the curing agent is a phenolic curing agent
  • the ratio of the active hydrogen equivalent of the phenolic hydroxyl group (phenolic hydroxyl group equivalent) to the epoxy equivalent of the mesogen-containing epoxy resin (phenolic hydroxyl group equivalent / epoxy equivalent) is 0. 0.5 to 2 is preferable, and 0.8 to 1.2 is more preferable.
  • the kind and compounding quantity of a hardening accelerator are not specifically limited, An appropriate thing can be selected from viewpoints, such as reaction rate, reaction temperature, and storage property.
  • Specific examples of the curing accelerator include imidazole compounds, organic phosphorus compounds, tertiary amines, and quaternary ammonium salts. 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 And alkyldiarylphosphine.
  • an organic phosphine compound and an organic boron compound include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetra-p-tolylborate, tetrabutylphosphonium / tetraphenylborate, and tetraphenylphosphonium.
  • 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 resin composition and a cured resin composition described later there is a method in which two kinds of curing accelerators having different reaction initiation temperatures and reaction rates between an epoxy resin monomer and a phenol novolac resin are mixed and used. Can be mentioned.
  • the mixing ratio can be determined without any particular limitation depending on the characteristics (for example, how much flexibility is required) required for the semi-cured resin composition. it can.
  • the content of the curing accelerator in the resin composition is not particularly limited. From the viewpoint of moldability, it is preferably 0.5% by mass to 1.5% by mass, and preferably 0.5% by mass to 1% by mass of the total mass of the thermosetting resin having a mesogenic group in the molecule and the curing agent. More preferably, it is more preferably 0.75% by mass to 1% by mass.
  • the 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 a role of forming a covalent bond between the surface of the first filler or the second filler and the thermosetting resin surrounding the surface (equivalent to a binder agent), and heat This also contributes to the improvement of insulation reliability by preventing the penetration of moisture.
  • the type of the silane coupling agent is not particularly limited, and a commercially available product may be used.
  • a commercially available product may be used.
  • a silane coupling agent having an epoxy group, amino group, mercapto group, ureido group, or hydroxyl group at the terminal.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane.
  • silane coupling agent oligomers (manufactured by Hitachi Chemical Coated Sand Co., Ltd.) represented by SC-6000KS2 can also be mentioned. These silane coupling agents may be used alone or in combination of two or more.
  • the resin composition may further contain at least one organic solvent.
  • an organic solvent By including an organic solvent, it can be adapted to various molding processes.
  • a commonly used organic solvent can be used. Specific examples include alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents, and the like.
  • methyl isobutyl ketone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, sulfolane, cyclohexanone, methyl ethyl ketone and the like can be used. These may be used alone or as a mixed solvent using two or more kinds in combination.
  • the resin composition in the present invention can contain other components as necessary in addition to the above components.
  • an elastomer, a dispersing agent, etc. are mentioned.
  • the elastomer include an acrylic resin, and more specifically, a homopolymer or a copolymer derived from (meth) acrylic acid or a (meth) acrylic ester.
  • the dispersant include Ajinomoto Finetech Co., Ltd. Ajisper series, Enomoto Kasei Co., Ltd. HIPLAAD series, Kao Corporation homogenol series, and the like. Two or more kinds of these dispersants can be used in combination.
  • the semi-cured resin composition of the present invention is derived from the resin composition, and is obtained by semi-curing the resin composition. For example, when the semi-cured resin composition is molded into a sheet, the handleability is improved as compared with a resin sheet made of a resin composition that is not semi-cured.
  • the semi-cured resin composition means that the viscosity of the semi-cured resin composition is 10 4 Pa ⁇ s to 10 5 Pa ⁇ s at room temperature (25 to 30 ° C.), whereas the viscosity is 100 ° C. Then, it has a feature that it is reduced to 10 2 Pa ⁇ s to 10 3 Pa ⁇ s. Moreover, the cured resin composition after curing described later is not melted 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 in which the resin composition is heated at a temperature of 100 ° C. to 200 ° C. for 1 minute to 30 minutes.
  • the cured resin composition of the present invention is derived from the resin composition, and is obtained by curing the resin composition.
  • the cured resin composition is excellent in thermal conductivity and insulation. This may be because, for example, a higher-order structure is formed as a result of combining a thermosetting resin having a mesogenic group in a molecule contained in the resin composition with a specific filler.
  • the cured resin composition can be produced by curing the uncured resin composition or the semi-cured resin composition.
  • the method for the curing treatment can be appropriately selected according to the composition of the resin composition, the purpose of the cured resin composition, and the like, but is preferably a heating / pressurizing treatment.
  • an uncured resin composition or the semi-cured 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. Is obtained.
  • the resin sheet of the present invention is formed by molding the resin composition into a sheet shape.
  • the said resin sheet can be manufactured by apply
  • the resin sheet is excellent in thermal conductivity, fluidity, and flexibility.
  • 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 viewpoints of thermal conductivity, electrical insulation, and flexibility.
  • the resin sheet is, for example, a varnish-like resin composition (hereinafter referred to as “resin varnish”) prepared by adding an organic solvent such as methyl ethyl ketone or cyclohexanone to the resin composition on a release film such as a PET film.
  • resin varnish a varnish-like resin composition
  • an organic solvent such as methyl ethyl ketone or cyclohexanone
  • 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.
  • a coating method for forming the resin composition layer with a predetermined thickness a comma coating method in which an object to be coated is passed between gaps, a die coating method in which a resin varnish whose flow rate is adjusted from a nozzle, or the like 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 resin composition layer of the resin sheet Since the resin composition layer of the resin sheet has almost no curing reaction, it has flexibility, but it has poor flexibility as a sheet, and in the state in which the PET film as a support is removed, the sheet is self-supporting. It is scarce and difficult to handle.
  • the resin sheet is preferably a semi-cured resin composition obtained by semi-curing a 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 resin composition obtained by semi-curing the resin composition, it has excellent thermal conductivity and electrical insulation, and is flexible and usable as a B-stage sheet. Excellent.
  • the viscosity of the B stage sheet is 10 4 Pa ⁇ s to 10 5 Pa ⁇ s at room temperature (25 to 30 ° C.), whereas it is 10 2 Pa ⁇ s to 10 3 at 100 ° C. It has a feature of lowering to Pa ⁇ s. Moreover, the cured 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 resin composition layer can be in a B-stage state, and can be appropriately selected according to the configuration of the 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 composition layer generated during coating. Thereby, a flat B stage sheet
  • the resin composition is heated and pressurized under reduced pressure (for example, 1 kPa) at a temperature of 100 ° C. to 200 ° C. for 1 second to 90 seconds with a press pressure of 1 MPa to 20 MPa. It can be semi-cured to the stage state.
  • reduced pressure for example, 1 kPa
  • the cured resin composition produced by the method described later is made to have higher thermal conductivity by laminating two coated / dried resin sheets and performing the above heating / pressurizing treatment. Indicates the rate. At this time, it is necessary to bond the application surfaces (the surfaces on the upper side during application, that is, the surfaces opposite to the surfaces in contact with the PET film), whereby both sides of the resin sheet become flatter.
  • 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. From the viewpoint of thermal conductivity, electrical insulation, and flexibility, the thickness is 80 ⁇ m to 300 ⁇ m. Preferably there is. It can also be produced by hot pressing while laminating two or more resin sheets.
  • the solvent remaining rate in the B-stage sheet is 2.0% by mass or less from the viewpoint of concern about bubble formation during outgas generation during curing. It is preferable that it is 1.0 mass% or less, and it is further more preferable that it is 0.8 mass% or less.
  • the solvent residual rate is determined from the mass change 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 the area of the B stage sheet before and after pressing a sample obtained by punching a 10 mm square B stage sheet having a thickness of 200 ⁇ m for 1 minute under conditions of atmospheric pressure, temperature of 180 ° C. and pressing pressure of 15 MPa. Calculated as the rate of change.
  • the area change rate is obtained from the change rate of the area (number of pixels) after taking an external projection image of the sample with a scanner of 300 DPI or more, binarizing with image analysis software (AdobeAPhotoshop).
  • the resin sheet may be a cured resin composition obtained by curing the resin composition.
  • a resin sheet made of the cured resin composition can be produced by curing an uncured resin sheet or B-stage sheet.
  • the method for the curing treatment can be appropriately selected according to the composition of the resin composition, the purpose of the cured resin composition, and the like, but is preferably a heating / pressurizing treatment.
  • an uncured resin sheet or B stage sheet is heated at 100 ° C. to 250 ° C. for 1 hour to 10 hours, preferably 130 ° C. to 230 ° C. for 1 hour to 8 hours. Is obtained.
  • the heating is preferably performed while applying a pressure of 1 MPa to 20 MPa.
  • a method for producing a resin sheet comprising a cured resin composition having excellent thermal conductivity first, a roughened surface of a copper foil (thickness 80 ⁇ m to 120 ⁇ m) having a roughened surface on one side of a B stage sheet.
  • the B stage sheet and the copper foil are bonded together by heating and pressing at a pressure of 1 MPa to 20 MPa at a temperature of 130 ° C. to 230 ° C. for 3 minutes to 10 minutes.
  • the prepreg of the present invention comprises a fiber base material and the resin composition impregnated in the fiber base material. With such a configuration, a prepreg excellent in thermal conductivity and insulation is obtained.
  • the resin composition containing the ⁇ -alumina filler has improved thixotropy, and therefore can suppress sedimentation of the second filler in a coating process and an impregnation process described later. Therefore, the occurrence of the density distribution of the second filler in the thickness direction of the prepreg can be suppressed, and as a result, a prepreg excellent in thermal conductivity and insulation 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 printed wiring board, and a fiber base material such as a woven fabric or a nonwoven fabric is usually used. .
  • the opening of the fiber base material is not particularly limited. From the viewpoint of thermal conductivity and insulating properties, the mesh opening is preferably 5 times or more the average particle diameter (D50) of the second filler. Further, when the particle size distribution curve of the second filler has a plurality of peaks, the opening is more preferably 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, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyether ether ketone, polyether imide, polyether sulfone, carbon , Organic fibers such as cellulose, and mixed papers thereof.
  • glass fiber woven fabric is preferably used. Thereby, for example, when a printed wiring board is configured using a prepreg, a printed wiring board that is flexible and can be arbitrarily bent can be obtained. Furthermore, it becomes possible to reduce the dimensional change of the printed wiring board accompanying the temperature change or moisture absorption 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 resin composition in the prepreg is preferably 50% by mass to 99.9% by mass with respect to the total mass of the fiber base material and the resin composition.
  • the prepreg is produced by impregnating a fiber base material with the resin composition prepared 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 resin composition there is no particular limitation on the method for impregnating the fiber base material with the resin composition.
  • coating with a coating machine can be mentioned.
  • the prepreg may be used after the surface is smoothed in advance by hot pressing with a press or a roll laminator before being laminated or pasted.
  • 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 / 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 0 More preferably, it is 8 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 laminated board in this invention has a to-be-adhered material and the semi-hardened resin composition layer or hardened resin composition layer arrange
  • the semi-cured resin composition layer and the cured resin composition layer are derived from at least one selected from a resin composition layer composed of the resin composition, the resin sheet, and the prepreg. A layer and a cured resin composition layer.
  • adherend examples include metal foil and metal plate.
  • the adherend may be attached to only one surface of the semi-cured resin composition layer or the cured resin composition layer, or may be attached to both surfaces.
  • 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 a high thermal conductivity and a large heat capacity. Specific examples include copper, aluminum, iron, and alloys used for lead frames.
  • 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 aluminum when priority is given to weight reduction and workability, and copper when priority is given to heat dissipation.
  • the said laminated board even if it is a form which has 1 layer derived from any one of the said resin composition layer, the said resin sheet, or the said prepreg as a semi-hardened resin composition layer or a cured resin composition layer.
  • a form in which two or more layers are stacked may be used.
  • it has two or more semi-cured resin composition layers or cured resin composition layers, it has a form having two or more resin composition layers, a form having two or more resin sheets, and two or more prepregs. Any form may be sufficient.
  • the laminated plate is formed by applying the resin composition on an adherend to form a resin composition layer, and heating and pressurizing the layer to semi-harden or cure the resin composition layer. It is obtained by making it adhere to an adherend. Alternatively, it is obtained by preparing a laminate of the resin sheet or the prepreg on the adherend and heating and pressurizing it to make the resin sheet or the prepreg semi-cured or cured and to adhere to the adherend. It is done.
  • the curing method for semi-curing or curing the 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 20 MPa, preferably in the range of 1 MPa to 15 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, the tendency is more visible. Further, when the thickness is 100 ⁇ m or more, the workability is excellent.
  • the resin cured product with metal foil is constituted by using two metal foils as adherends in the laminate. Specifically, one metal foil, the cured resin composition layer, and the other metal foil are laminated in this order. Details of the metal foil and the cured resin composition layer constituting the cured resin product 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 resin composition layer, and the metal plate in this order. Details of the metal foil and the cured 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 printed wiring board of the present invention is formed by laminating a metal plate, a cured resin composition layer, and a wiring layer in this order.
  • the cured resin composition layer is a cured resin composition layer derived from at least one selected from a resin composition layer composed of the resin composition, the resin sheet, and the prepreg.
  • the printed wiring board can be produced by subjecting at least one metal foil in the resin cured product with metal foil described above or a 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 printed wiring board include those similar to the printed wiring board described in paragraph No. 0064 of JP2009-214525A and paragraph Nos. 0056 to 0059 of JP2009-275086A. it can.
  • the power semiconductor device of the present invention is a semiconductor module in which a metal plate, a solder layer, and a semiconductor chip are laminated in this order, a heat dissipation member, and the present invention disposed between the metal plate and the heat dissipation member of the semiconductor module. And a cured product of a resin sheet which is a sheet-like molded body of the resin composition.
  • the semiconductor module portion may be sealed with a sealing material or the like, or the entire power semiconductor module may be molded with a molding resin or the like.
  • FIG. 11 is a schematic cross-sectional view showing an example of the configuration of the power semiconductor device.
  • a cured body 102 of a resin sheet is disposed between a metal plate 106 and a heat dissipation base substrate 104 in a semiconductor module in which a metal plate 106, a solder layer 110, and a semiconductor chip 108 are laminated in this order. These parts are sealed with a sealing material 114.
  • FIG. 12 is a schematic cross-sectional view showing another example of the configuration of the power semiconductor device. In FIG.
  • a resin sheet cured body 102 is disposed between the metal plate 106 and the heat dissipation base substrate 104 in the semiconductor module in which the metal plate 106, the solder layer 110, and the semiconductor chip 108 are laminated in this order, and the semiconductor module. And the heat dissipation base substrate 104 are molded with a mold resin 112.
  • the cured body of the resin sheet which is a sheet-like molded body of the resin composition of the present invention, can be used as a heat-dissipating adhesive layer between the semiconductor module and the heat-dissipating base substrate as shown in FIG. is there. Even when the entire power semiconductor device is molded as shown in FIG. 12, it can be used as a heat dissipation material between the heat dissipation base substrate and the metal plate.
  • the obtained CRN was measured for Mn and Mw as follows.
  • Mn and 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 the measurement was performed at a flow rate of 1.0 ml / min.
  • a calibration curve was prepared using a polystyrene standard sample, and Mn and Mw were calculated using polystyrene conversion values.
  • the hydroxyl equivalent was measured as follows.
  • the hydroxyl equivalent was measured by acetyl chloride-potassium hydroxide titration method.
  • the determination of the titration end point was performed by potentiometric titration instead of the coloring method using an indicator because the solution color was dark.
  • the hydroxyl group of the measurement resin is acetylated in a pyridine solution, the excess reagent is decomposed with water, and the resulting acetic acid is titrated with a potassium hydroxide / methanol solution.
  • the obtained CRN is shown below.
  • a mixture of compounds having a partial structure represented by at least one of general formulas (II-1) to (II-4), wherein Ar is R 11 hydroxyl group in general formula (II-a)
  • TPP Triphenylphosphine [curing accelerator]
  • KBM-573 3-phenylaminopropyltrimethoxysilane [Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.]
  • Example 1 Preparation of resin composition> First filler ( ⁇ -alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 70.29% by mass, thermosetting resin (resin A) 10.22% by mass Curing agent (CRN) 6.30% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 12.56% by mass.
  • An epoxy resin varnish was obtained as a resin composition containing a solvent.
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 . It was 0.26 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening
  • thermosetting resin (Cured resin without filler)
  • the mixture of the thermosetting resin, the curing agent, and the curing accelerator used for the preparation of the resin composition was melted and sandwiched between two aluminum plates (thickness: 200 ⁇ m), and the pressure was 1 at 140 ° C. under atmospheric pressure conditions. Heating was performed for 1 hour at 165 ° C. for 1 hour and further at 190 ° C. for 1 hour to obtain a resin-cured product without filler with aluminum plate (thickness: about 150 ⁇ m).
  • the thermal diffusivity of the cured resin product obtained by peeling the aluminum plate from the filler-free resin cured product with an aluminum plate was evaluated using a temperature wave thermal analyzer (ai-Phase mobile 1u manufactured by ai-Phase). From this value and the product of the density and specific heat obtained by the above-mentioned method, the thermal conductivity of the resin-free cured resin is obtained, and this is the thermal conductivity of the resin part in the cured resin sheet (cured resin composition). Rate.
  • Table 1 The results are shown in Table 1.
  • Example 2 First filler ( ⁇ -alumina, mixture of HIT-70: 0.45 vol% and AA-04: 11.76 vol%) 12.21% by mass, second filler (boron nitride, HP-40) 58 .53 mass%, thermosetting resin (resin A) 10.22 mass%, curing agent (CRN) 6.30 mass%, curing accelerator (TPP) 0.11 mass%, silane coupling agent (KBM-573) ) 0.07% by mass and 12.56% by mass of solvent (CHN) were mixed to obtain an epoxy resin varnish as a resin composition containing the solvent.
  • thermosetting resin resin A
  • CCN curing agent
  • TPP curing accelerator
  • KBM-573 silane coupling agent
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 . It was 7.5 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening
  • a B stage sheet and a cured resin product with a copper foil 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 First filler ( ⁇ -alumina, HIT-70) 0.45% by mass, second filler 63.84% by mass (aluminum nitride, FAN-f30: 49.02% by volume and FAN-f05: 14.82% by volume) % Filler), third filler (aluminum nitride, ShapalH) 10.39 mass%, thermosetting resin (resin A) 7.23 mass%, curing agent (CRN) 4.46 mass%, curing accelerator ( TPP) 0.08% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 13.48% by mass were mixed to obtain an epoxy resin varnish as a resin composition containing the solvent. .
  • the density of the alumina is 3.97 g / cm 3
  • the density of aluminum nitride is 3.26 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 .
  • the ratio of the total volume of the 2nd filler and the 3rd filler with respect to the said total volume was 74 volume%.
  • the average particle diameter (D50) of the 2nd filler was 24 micrometers.
  • the hot press conditions by vacuum press were changed to press temperature: 150 ° C., vacuum degree: 1 kPa, press pressure: 1 MPa, treatment time: 60 seconds, and by vacuum press.
  • the B-stage sheet and the resin with copper foil were the same as in Example 1 except that the vacuum pressure bonding conditions were changed to press temperature: 150 ° C., vacuum degree: 1 kPa, press pressure: 4 MPa, treatment time: 5 minutes.
  • a cured product was prepared and evaluated in the same manner as described above. The results are shown in Table 1.
  • Example 4 First filler ( ⁇ -alumina, HIT-70) 0.45 mass%, second filler (boron nitride, HP-40) 70.29 mass%, thermosetting resin (resin B) 10.22 mass% Curing agent (CRN) 6.30% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 12.56% by mass.
  • An epoxy resin varnish was obtained as a resin composition containing a solvent.
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 . It was 0.26 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening
  • a B stage sheet and a cured resin product with a copper foil 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 First filler ( ⁇ -alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 70.29% by mass, thermosetting resin (resin C) 10.34% by mass , Curing agent (CRN) 6.05% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 12.69% by mass.
  • An epoxy resin varnish was obtained as a resin composition containing a solvent.
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 . It was 0.26 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening
  • a B stage sheet and a cured resin product with a copper foil 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 6 First filler ( ⁇ -alumina, HIT-70) 0.45 mass%, second filler (boron nitride, HP-40) 70.29 mass%, thermosetting resin (resin D) 10.42 mass% A curing agent (CRN) of 5.90% by mass, a curing accelerator (TPP) of 0.11% by mass, a silane coupling agent (KBM-573) of 0.07% by mass, and a solvent (CHN) of 12.76% by mass. An epoxy resin varnish was obtained as a resin composition containing a solvent.
  • CRN curing agent
  • TPP curing accelerator
  • KBM-573 silane coupling agent
  • CHN solvent
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 . It was 0.26 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening
  • a B stage sheet and a cured resin product with a copper foil 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 7 First filler ( ⁇ -alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 74.23% by mass, thermosetting resin (resin A) 7.23% by mass Curing agent (CRN) 4.46% by mass, curing accelerator (TPP) 0.08% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 13.48% by mass.
  • An epoxy resin varnish was obtained as a resin composition containing a solvent.
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 . It was 0.27 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening
  • a B stage sheet and a cured resin product with a copper foil 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.
  • Second filler (boron nitride, HP-40) 70.61% by mass, thermosetting resin (resin A) 10.26% by mass, curing agent (CRN) 6.34% by mass, curing accelerator (TPP) 0 .11 mass%, silane coupling agent (KBM-573) 0.07 mass%, and solvent (CHN) 12.61 mass% were mixed to obtain an epoxy resin varnish as a resin composition containing a solvent.
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of resin A and CRN is 1.20 g / cm 3
  • the proportion of the filler was calculated to be 74% by volume.
  • a B stage sheet and a cured resin product with a copper foil 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 2.
  • Density 2.20 g / cm 3 of silica, the density of boron nitride 2.18 g / cm 3, and the density of the mixture of the resin A and the CRN as 1.20 g / cm 3, a silica nanofiller and a second filler It was 0.26 volume% when the ratio of the silica nanofiller with respect to the total volume of a thermosetting resin and a hardening
  • a B stage sheet and a cured resin product with a copper foil 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 2.
  • the density of the alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of Resin A and CRN is 1.20 g / cm 3 .
  • the ratio of the ⁇ -alumina filler to the total volume of the filler, thermosetting resin and curing agent was calculated to be 0.40% by volume. Moreover, it was 69 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.
  • a B stage sheet and a cured resin product with a copper foil 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 2.
  • the density of alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of resin A and CRN is 1.20 g / cm 3
  • the ⁇ -alumina nanofiller and the second The ratio of ⁇ -alumina nanofiller to the total volume of the filler, thermosetting resin and curing agent was calculated to be 0.26% by volume. Moreover, it was 74 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.
  • a B stage sheet and a cured resin product with a copper foil 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 2.
  • the density of alumina is 3.97 g / cm 3
  • the density of boron nitride is 2.18 g / cm 3
  • the density of the mixture of bisphenol A type epoxy resin and CRN is 1.20 g / cm 3
  • a B stage sheet and a cured resin product with a copper foil 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 2. In Tables 1 and 2, “-” indicates no addition.
  • the cured resin sheets of Examples 1 to 7 all showed high thermal conductivity. Further, in any of Examples 1 to 7, the thermal conductivity of the cured resin converted from the cured resin sheet is higher than the thermal conductivity of the cured resin obtained from the cured resin without filler. Indicated. From this, it was proved that the thermosetting resin having a mesogenic group exhibits higher order with the alumina filler as a nucleus, and the thermal conductivity of the cured resin itself is improved. In each of Examples 1 to 7, both the flow amount and the dielectric breakdown voltage were good.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)
  • Cooling Or The Like Of Electrical Apparatus (AREA)
PCT/JP2012/078222 2011-11-02 2012-10-31 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置 WO2013065758A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020147013363A KR101958506B1 (ko) 2011-11-02 2012-10-31 수지 조성물, 및 그것을 이용한 수지 시트, 프리프레그, 적층판, 금속 기판, 프린트 배선판 및 파워 반도체 장치
JP2013541828A JP6102744B2 (ja) 2011-11-02 2012-10-31 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置
CN201280053424.3A CN104024332A (zh) 2011-11-02 2012-10-31 树脂组合物、以及使用该树脂组合物的树脂片、预浸料坯、层叠板、金属基板、印刷配线板和功率半导体装置

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/JP2011/075345 WO2013065159A1 (ja) 2011-11-02 2011-11-02 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板及びプリント配線板
JPPCT/JP2011/075345 2011-11-02
JP2012090473 2012-04-11
JP2012-090473 2012-04-11

Publications (1)

Publication Number Publication Date
WO2013065758A1 true WO2013065758A1 (ja) 2013-05-10

Family

ID=48192098

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/078222 WO2013065758A1 (ja) 2011-11-02 2012-10-31 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置

Country Status (5)

Country Link
JP (3) JP6102744B2 (ko)
KR (1) KR101958506B1 (ko)
CN (2) CN109293883A (ko)
TW (3) TWI616334B (ko)
WO (1) WO2013065758A1 (ko)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015136806A1 (ja) * 2014-03-10 2015-09-17 日東電工株式会社 熱伝導性ポリマー組成物及び熱伝導性成形体
WO2015166609A1 (ja) * 2014-04-30 2015-11-05 日東電工株式会社 熱伝導性ポリマー組成物及び熱伝導性成形体
KR20150140224A (ko) * 2014-06-05 2015-12-15 신에쓰 가가꾸 고교 가부시끼가이샤 열경화성 수지 조성물
WO2016093248A1 (ja) * 2014-12-08 2016-06-16 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、樹脂付金属箔、金属基板、及びパワー半導体装置
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
JP2017101257A (ja) * 2011-11-02 2017-06-08 日立化成株式会社 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置
WO2018173953A1 (ja) * 2017-03-24 2018-09-27 東レ株式会社 プリプレグおよび炭素繊維強化複合材料
JP6399176B1 (ja) * 2017-09-15 2018-10-03 東洋インキＳｃホールディングス株式会社 熱伝導性絶縁シートおよび複合部材
JP2019123799A (ja) * 2018-01-16 2019-07-25 日立化成株式会社 層間絶縁層用樹脂組成物、層間絶縁層用樹脂フィルム、多層プリント配線板、半導体パッケージ及び多層プリント配線板の製造方法
JP2020045422A (ja) * 2018-09-19 2020-03-26 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
WO2020256005A1 (ja) * 2019-06-21 2020-12-24 住友ベークライト株式会社 熱硬化性樹脂組成物、樹脂シートおよび金属ベース基板
WO2024062923A1 (ja) * 2022-09-21 2024-03-28 東レ株式会社 フィルム、積層体、プラズマ処理装置、及び積層体の製造方法

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5849176B1 (ja) * 2014-02-12 2016-01-27 日本碍子株式会社 半導体用複合基板のハンドル基板および半導体用複合基板
CN107109161B (zh) * 2014-11-12 2019-07-02 迪睿合株式会社 热固化性粘合组合物
JP6669080B2 (ja) * 2014-12-15 2020-03-18 日立化成株式会社 エポキシ樹脂成形材料、成形物及び成形硬化物
JP6503725B2 (ja) * 2014-12-15 2019-04-24 日立化成株式会社 エポキシ樹脂組成物、樹脂シート、半硬化エポキシ樹脂組成物、硬化エポキシ樹脂組成物及び金属基板
TWI748935B (zh) 2014-12-26 2021-12-11 日商昭和電工材料股份有限公司 環氧樹脂、環氧樹脂組成物、含無機塡料的環氧樹脂組成物、樹脂薄片、硬化物、及環氧化合物
WO2016121758A1 (ja) * 2015-01-29 2016-08-04 日立化成株式会社 エポキシ樹脂組成物、半硬化エポキシ樹脂組成物、樹脂シート及びプリプレグ
JP6646360B2 (ja) * 2015-04-24 2020-02-14 日東電工株式会社 封止用樹脂シート、及び、電子デバイス装置
US10584228B2 (en) * 2015-05-22 2020-03-10 Hitachi Chemical Company, Ltd. Epoxy resin composition, thermally-conductive material precursor, B-stage sheet, prepreg, heat dissipation material, laminate, metal substrate, and printed circuit board
WO2017145410A1 (ja) * 2016-02-25 2017-08-31 日立化成株式会社 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、成形物及び成形硬化物
WO2017145413A1 (ja) * 2016-02-25 2017-08-31 日立化成株式会社 エポキシ樹脂組成物、樹脂シート、ｂステージシート、ｃステージシート、硬化物、樹脂付金属箔及び金属基板
WO2017145412A1 (ja) * 2016-02-25 2017-08-31 日立化成株式会社 樹脂シート及び樹脂シート硬化物
KR102423947B1 (ko) * 2016-02-25 2022-07-21 쇼와덴코머티리얼즈가부시끼가이샤 에폭시 수지 성형 재료, 성형물, 성형 경화물, 및 성형 경화물의 제조 방법
WO2017209209A1 (ja) * 2016-06-02 2017-12-07 日立化成株式会社 積層体の製造方法
US11149109B2 (en) 2016-06-22 2021-10-19 Showa Denko Materials Co., Ltd. Epoxy resin composition, cured product and composite material
CN107978586B (zh) * 2016-10-25 2019-11-26 上海新昇半导体科技有限公司 校准晶片及其制造方法
US11535700B2 (en) 2017-03-09 2022-12-27 Showa Denko Materials Co., Ltd. Epoxy polymer, epoxy resin, epoxy resin composition, resin sheet, b-stage sheet, cured product, c-stage sheet, metal foil with resin, metal substrate and method for manufacturing
WO2018174446A1 (ko) * 2017-03-22 2018-09-27 주식회사 엘지화학 반도체 패키지용 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
WO2018174447A1 (ko) * 2017-03-22 2018-09-27 주식회사 엘지화학 반도체 패키지용 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
KR102057255B1 (ko) 2017-03-22 2019-12-18 주식회사 엘지화학 반도체 패키지용 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
KR102049024B1 (ko) * 2017-03-22 2019-11-26 주식회사 엘지화학 반도체 패키지용 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
JP7279303B2 (ja) * 2017-05-10 2023-05-23 味の素株式会社 樹脂組成物層
KR20200034967A (ko) * 2017-07-28 2020-04-01 도레이 카부시키가이샤 프리프레그 및 탄소섬유 강화 복합 재료
TW201922909A (zh) * 2017-09-22 2019-06-16 日商日立化成股份有限公司 帶保護材的厚銅電路
US20210238465A1 (en) * 2018-06-06 2021-08-05 Showa Denko K.K. Method of producing glass-coated aluminum nitride particles and method of producing heat-dissipating resin composition comprising these glass-coated aluminum nitride particles
EP3901191A4 (en) * 2018-12-21 2022-08-24 Nitto Shinko Corporation RESIN COMPOSITION
US20220153920A1 (en) * 2019-02-14 2022-05-19 Nissan Chemical Corporation Method for producing polymer
JP7167310B2 (ja) * 2019-03-27 2022-11-08 富士フイルム株式会社 放熱シートの製造方法
WO2020194920A1 (ja) * 2019-03-27 2020-10-01 日本発條株式会社 熱硬化性エポキシ樹脂組成物、回路基板用積層板、金属ベース回路基板、およびパワーモジュール
JP7466951B2 (ja) * 2019-08-19 2024-04-15 エルジー・ケム・リミテッド 樹脂組成物
CN115066465A (zh) * 2020-02-06 2022-09-16 富士胶片株式会社 组合物、导热材料、导热片及带导热层的器件
KR102297770B1 (ko) * 2020-12-10 2021-09-03 (주)테라시스 기능성 시트 및 이의 제조 방법
WO2023068024A1 (ja) * 2021-10-20 2023-04-27 株式会社有沢製作所 熱硬化性樹脂組成物、放熱シート、放熱板、放熱シートの製造方法、及び放熱板の製造方法
TWI831247B (zh) * 2022-06-16 2024-02-01 先豐通訊股份有限公司 功率模組及其製作方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002047009A (ja) * 2000-05-23 2002-02-12 Sumitomo Chem Co Ltd αアルミナ粉末およびそれを用いた熱伝導性シート
WO2009136508A1 (ja) * 2008-05-08 2009-11-12 富士高分子工業株式会社 熱伝導性樹脂組成物
JP2011012193A (ja) * 2009-07-03 2011-01-20 Denki Kagaku Kogyo Kk 樹脂組成物及びその用途
WO2011040416A1 (ja) * 2009-09-29 2011-04-07 日立化成工業株式会社 樹脂組成物、樹脂シート、ならびに、樹脂硬化物およびその製造方法
JP2011074366A (ja) * 2009-09-03 2011-04-14 Sumitomo Chemical Co Ltd ジエポキシ化合物、該化合物を含む組成物及び該組成物を硬化して得られる硬化物

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007308640A (ja) * 2006-05-19 2007-11-29 Kyocera Chemical Corp 積層板用樹脂組成物、有機基材プリプレグ、金属張積層板およびプリント配線板
JP5064842B2 (ja) * 2007-03-07 2012-10-31 電気化学工業株式会社 金属箔、それを用いた金属ベース回路基板、金属ベース多層回路基板の製造方法
WO2011034114A1 (ja) * 2009-09-17 2011-03-24 住友化学株式会社 ジエポキシ化合物、その製造方法および該ジエポキシ化合物を含む組成物
KR101683355B1 (ko) * 2009-09-29 2016-12-06 히타치가세이가부시끼가이샤 다층 수지 시트 및 그 제조 방법, 다층 수지 시트 경화물의 제조 방법, 그리고, 고열전도 수지 시트 적층체 및 그 제조 방법
JP5513840B2 (ja) * 2009-10-22 2014-06-04 電気化学工業株式会社 絶縁シート、回路基板及び絶縁シートの製造方法
JP2011246440A (ja) * 2010-04-27 2011-12-08 Sumitomo Chemical Co Ltd ジエポキシ化合物及びその製造方法、並びに、該化合物を硬化して得られる硬化物
JP2012111927A (ja) * 2010-11-02 2012-06-14 Sumitomo Chemical Co Ltd 組成物及び該組成物を硬化して得られる硬化物
KR101929067B1 (ko) * 2011-01-25 2018-12-13 히타치가세이가부시끼가이샤 수지 조성물 시트, 금속박이 부착된 수지 조성물 시트, 메탈 베이스 배선판 재료, 메탈 베이스 배선판, 및 ｌｅｄ 광원 부재
CN109293883A (zh) * 2011-11-02 2019-02-01 日立化成株式会社 树脂组合物及树脂片、预浸料坯、层叠板、金属基板、印刷配线板和功率半导体装置
JP5928477B2 (ja) * 2011-11-02 2016-06-01 日立化成株式会社 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板及びプリント配線板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002047009A (ja) * 2000-05-23 2002-02-12 Sumitomo Chem Co Ltd αアルミナ粉末およびそれを用いた熱伝導性シート
WO2009136508A1 (ja) * 2008-05-08 2009-11-12 富士高分子工業株式会社 熱伝導性樹脂組成物
JP2011012193A (ja) * 2009-07-03 2011-01-20 Denki Kagaku Kogyo Kk 樹脂組成物及びその用途
JP2011074366A (ja) * 2009-09-03 2011-04-14 Sumitomo Chemical Co Ltd ジエポキシ化合物、該化合物を含む組成物及び該組成物を硬化して得られる硬化物
WO2011040416A1 (ja) * 2009-09-29 2011-04-07 日立化成工業株式会社 樹脂組成物、樹脂シート、ならびに、樹脂硬化物およびその製造方法

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017101257A (ja) * 2011-11-02 2017-06-08 日立化成株式会社 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置
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
WO2015136806A1 (ja) * 2014-03-10 2015-09-17 日東電工株式会社 熱伝導性ポリマー組成物及び熱伝導性成形体
WO2015166609A1 (ja) * 2014-04-30 2015-11-05 日東電工株式会社 熱伝導性ポリマー組成物及び熱伝導性成形体
US10544341B2 (en) 2014-04-30 2020-01-28 Nitto Denko Corporation Thermally conductive polymer composition and thermally conductive molded object
JP2016011410A (ja) * 2014-06-05 2016-01-21 信越化学工業株式会社 熱硬化性樹脂組成物
KR102383874B1 (ko) * 2014-06-05 2022-04-08 신에쓰 가가꾸 고교 가부시끼가이샤 열경화성 수지 조성물
KR20150140224A (ko) * 2014-06-05 2015-12-15 신에쓰 가가꾸 고교 가부시끼가이샤 열경화성 수지 조성물
WO2016093248A1 (ja) * 2014-12-08 2016-06-16 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、樹脂付金属箔、金属基板、及びパワー半導体装置
JPWO2016093248A1 (ja) * 2014-12-08 2017-09-21 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、樹脂付金属箔、金属基板、及びパワー半導体装置
JP7201029B2 (ja) 2014-12-08 2023-01-10 昭和電工マテリアルズ株式会社 エポキシ樹脂組成物、樹脂シート、プリプレグ、樹脂付金属箔、金属基板、及びパワー半導体装置
JP2021165401A (ja) * 2014-12-08 2021-10-14 昭和電工マテリアルズ株式会社 エポキシ樹脂組成物、樹脂シート、プリプレグ、樹脂付金属箔、金属基板、及びパワー半導体装置
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
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
JPWO2017010403A1 (ja) * 2015-07-10 2018-02-15 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
JPWO2018173953A1 (ja) * 2017-03-24 2019-03-28 東レ株式会社 プリプレグおよび炭素繊維強化複合材料
US11319420B2 (en) 2017-03-24 2022-05-03 Toray Industries, Inc. Prepreg and carbon fiber reinforced composite material
WO2018173953A1 (ja) * 2017-03-24 2018-09-27 東レ株式会社 プリプレグおよび炭素繊維強化複合材料
KR20200054216A (ko) 2017-09-15 2020-05-19 토요잉크Sc홀딩스주식회사 열 전도성 절연 시트 및 복합 부재
WO2019054486A1 (ja) * 2017-09-15 2019-03-21 東洋インキＳｃホールディングス株式会社 熱伝導性絶縁シートおよび複合部材
JP6399176B1 (ja) * 2017-09-15 2018-10-03 東洋インキＳｃホールディングス株式会社 熱伝導性絶縁シートおよび複合部材
JP2019052264A (ja) * 2017-09-15 2019-04-04 東洋インキＳｃホールディングス株式会社 熱伝導性絶縁シートおよび複合部材
KR102493229B1 (ko) 2017-09-15 2023-01-31 토요잉크Sc홀딩스주식회사 열 전도성 절연 시트 및 복합 부재
US11825632B2 (en) 2017-09-15 2023-11-21 Toyo Ink Sc Holdings Co., Ltd. Thermally conductive insulating sheet, and composite member
JP2019123799A (ja) * 2018-01-16 2019-07-25 日立化成株式会社 層間絶縁層用樹脂組成物、層間絶縁層用樹脂フィルム、多層プリント配線板、半導体パッケージ及び多層プリント配線板の製造方法
JP2020045422A (ja) * 2018-09-19 2020-03-26 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
JP7154479B2 (ja) 2018-09-19 2022-10-18 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
WO2020256005A1 (ja) * 2019-06-21 2020-12-24 住友ベークライト株式会社 熱硬化性樹脂組成物、樹脂シートおよび金属ベース基板
JPWO2020256005A1 (ja) * 2019-06-21 2021-09-13 住友ベークライト株式会社 熱硬化性樹脂組成物、樹脂シートおよび金属ベース基板
CN113993947A (zh) * 2019-06-21 2022-01-28 住友电木株式会社 热固性树脂组合物、树脂片及金属基基板
WO2024062923A1 (ja) * 2022-09-21 2024-03-28 東レ株式会社 フィルム、積層体、プラズマ処理装置、及び積層体の製造方法

Also Published As

Publication number Publication date
JP6171310B2 (ja) 2017-08-02
TW201333089A (zh) 2013-08-16
JP6304419B2 (ja) 2018-04-04
JP6102744B2 (ja) 2017-03-29
TW201720657A (zh) 2017-06-16
KR20140087015A (ko) 2014-07-08
JPWO2013065758A1 (ja) 2015-04-02
CN109293883A (zh) 2019-02-01
TWI577720B (zh) 2017-04-11
KR101958506B1 (ko) 2019-03-14
TW201811561A (zh) 2018-04-01
TWI616334B (zh) 2018-03-01
JP2013234313A (ja) 2013-11-21
CN104024332A (zh) 2014-09-03
JP2017101257A (ja) 2017-06-08

Similar Documents

Publication Publication Date Title
JP6304419B2 (ja) 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置
JP5928477B2 (ja) 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板及びプリント配線板
JP6311820B2 (ja) 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
JP7201029B2 (ja) エポキシ樹脂組成物、樹脂シート、プリプレグ、樹脂付金属箔、金属基板、及びパワー半導体装置
JP6102082B2 (ja) 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、及びプリント配線板
JP6161864B2 (ja) 樹脂組成物、樹脂シート、プリプレグ、積層板、金属基板、及びプリント配線板
JP5573842B2 (ja) 多層樹脂シート及びその製造方法、多層樹脂シート硬化物の製造方法、並びに、高熱伝導樹脂シート積層体及びその製造方法
JP2016155985A (ja) 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、及びそれらを用いた樹脂シート、プリプレグ、積層板、金属基板、配線板、パワー半導体装置
WO2016098709A1 (ja) 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
JP7115538B2 (ja) エポキシ樹脂、エポキシ樹脂組成物、樹脂シート、ｂステージシート、ｃステージシート、硬化物、樹脂付金属箔、金属基板、及びパワー半導体装置
WO2016121758A1 (ja) エポキシ樹脂組成物、半硬化エポキシ樹脂組成物、樹脂シート及びプリプレグ
JP6132041B2 (ja) 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板及びプリント配線板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12846501

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013541828

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20147013363

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 12846501

Country of ref document: EP

Kind code of ref document: A1