WO2022202792A1 - 熱硬化性樹脂組成物、高周波デバイス、誘電体基板、およびマイクロストリップアンテナ - Google Patents

熱硬化性樹脂組成物、高周波デバイス、誘電体基板、およびマイクロストリップアンテナ Download PDF

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WO2022202792A1
WO2022202792A1 PCT/JP2022/013094 JP2022013094W WO2022202792A1 WO 2022202792 A1 WO2022202792 A1 WO 2022202792A1 JP 2022013094 W JP2022013094 W JP 2022013094W WO 2022202792 A1 WO2022202792 A1 WO 2022202792A1
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Prior art keywords
resin composition
thermosetting resin
curing agent
active ester
epoxy resin
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PCT/JP2022/013094
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English (en)
French (fr)
Japanese (ja)
Inventor
俊次 木村
剛志 田中
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority to KR1020237036074A priority Critical patent/KR20230161473A/ko
Priority to CN202280024621.6A priority patent/CN117083345A/zh
Priority to JP2023509187A priority patent/JP7347713B2/ja
Publication of WO2022202792A1 publication Critical patent/WO2022202792A1/ja
Priority to JP2023135283A priority patent/JP2023179419A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—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
    • 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
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P3/00—Waveguides; Transmission lines of the waveguide type
    • H01P3/16—Dielectric waveguides, i.e. without a longitudinal conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q13/00—Waveguide horns or mouths; Slot antennas; Leaky-waveguide antennas; Equivalent structures causing radiation along the transmission path of a guided wave
    • H01Q13/08—Radiating ends of two-conductor microwave transmission lines, e.g. of coaxial lines, of microstrip lines
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium

Definitions

  • the present invention relates to thermosetting resin compositions, high frequency devices, dielectric substrates, and microstrip antennas.
  • Communication equipment can be made even more compact by increasing the dielectric constant of the antenna material (dielectric substrate) incorporated inside the communication equipment. Further, when the dielectric loss tangent of the dielectric substrate becomes small, the loss becomes low, which is advantageous for increasing the frequency. Therefore, if a dielectric substrate with a high dielectric constant and a small dielectric loss tangent can be used, it is possible to increase the frequency, shorten the circuit, and reduce the size of communication equipment.
  • Patent Document 1 describes a high dielectric constant resin composition containing an epoxy resin and a high dielectric constant inorganic filler such as strontium titanate (Claim 1, Table 2, etc.).
  • a dielectric substrate which is a composite material containing a fluororesin and a glass cloth, and an antenna having a two-dimensional roughness Ra of less than 0.2 ⁇ m on a surface in contact with the fluororesin, are disclosed.
  • An antenna having a substrate is disclosed.
  • the document describes the dielectric constant and dielectric loss tangent of the circuit board measured at 1 GHz.
  • Patent Document 3 discloses a resin composition containing a siloxane-modified polyamideimide resin, a high dielectric constant filler, and an epoxy resin, and having a cured product with a dielectric constant of 15 or more at 25°C and 1 MHz. Examples of the document describe an example of using barium titanate as the high dielectric constant filler.
  • Patent Document 4 discloses a resin composition containing an epoxy resin, a dielectric powder, a nonionic surfactant, and an active ester curing agent. This document describes that this resin composition can be used as a high dielectric constant insulating material for electronic parts used in a high frequency range and as a high dielectric constant insulating material for fingerprint sensors. Examples of the literature describe an example of using barium titanate as the dielectric powder.
  • Patent Document 5 discloses an epoxy resin, a curing agent, and an inorganic filler containing predetermined amounts of calcium titanate particles and strontium titanate particles, and the inorganic filler consists of silica particles and alumina particles.
  • a molding resin composition further containing at least one selected from the group and used for encapsulating electronic parts in high-frequency devices is disclosed.
  • Patent Documents 1 to 4 have room for improvement in the following points.
  • the resin composition described in Patent Document 1 it has been found that there is room for improvement in terms of void suppression and filling properties during molding of members, and shape retention and toughness of members. This is the first issue.
  • the dielectric substrates described in Patent Documents 2 to 5 have problems with high dielectric constant and low dielectric loss tangent, and these problems are particularly noticeable in a high frequency band. This is the second subject.
  • the present inventors highly filled the thermosetting resin composition with calcium titanate particles or strontium titanate particles as a high dielectric constant filler, and then adopted a combination of a predetermined epoxy resin and a predetermined curing agent.
  • the present inventors have found that the first problem can be solved by setting the bending elastic modulus and the rectangular pressure at 260°C within appropriate ranges, and completed the first invention. That is, the first invention can be shown below.
  • thermosetting resin composition comprising (B) a curing agent and (C) a high dielectric constant filler,
  • the high dielectric constant filler (C) contains 50% by mass or more of calcium titanate particles or 60% by mass or more of strontium titanate particles in 100% by mass of the solid content of the thermosetting resin composition
  • the epoxy resin (A) contains a biphenyl aralkyl epoxy resin and/or a biphenyl epoxy resin
  • the curing agent (B) contains an active ester compound (B1) and/or a phenolic curing agent (B2),
  • the active ester compound (B1) is an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolak, or an active ester containing a benzoylated phenol novolac.
  • the phenolic curing agent (B2) contains a biphenylaralkyl-type phenolic resin and/or a phenolic novolak resin
  • the flexural modulus at 260° C. measured according to procedure 1 below is 50 N/mm 2 or more and 190 N/mm 2 or less
  • the rectangular pressure measured according to the following procedure 2 is 0.2 MPa or more and 8.8 MPa or less.
  • a thermosetting resin composition is provided. (Step 1) The thermosetting resin composition is injection molded into a mold using a low-pressure transfer molding machine under the conditions of a mold temperature of 130 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. A molding with a height of 80 mm is obtained.
  • the resulting molded article is post-cured at 175° C. for 4 hours to prepare a test piece.
  • the flexural modulus (N/mm 2 ) of the test piece at 260°C is measured according to JIS K 6911.
  • Step 2 Using a low-pressure transfer molding machine, the thermosetting resin composition was poured into a rectangular channel having a width of 13 mm, a thickness of 1 mm, and a length of 175 mm under conditions of a mold temperature of 175°C and an injection rate of 177 mm 3 /sec. injected.
  • a pressure sensor embedded at a position 25 mm from the upstream end of the flow channel measures the change in pressure over time, measures the minimum pressure (MPa) at the time of flow of the thermosetting resin composition, and divides it into a rectangle. pressure.
  • a high-frequency device comprising a cured product of the above thermosetting resin composition.
  • thermosetting resin composition containing an epoxy resin, a curing agent, and a high dielectric constant filler includes a specific epoxy resin and an active ester curing agent as the curing agent in combination.
  • thermosetting resin composition comprising
  • the epoxy resin (A) is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, glycidylamine type epoxy resin, and naphthol aralkyl type epoxy resin.
  • the curing agent (B) contains an active ester curing agent (B1) and/or a phenolic curing agent (B2),
  • the high dielectric constant filler (C) is calcium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, zircon titanate.
  • a thermosetting resin composition comprising at least one selected from calcium acid, lead zirconate titanate, barium magnesium niobate, and calcium zirconate.
  • thermosetting resin composition A dielectric substrate obtained by curing the thermosetting resin composition is provided.
  • a microstrip antenna comprising:
  • a dielectric substrate a radiation conductor plate provided on one surface of the dielectric substrate; a ground conductor plate provided on the other surface of the dielectric substrate; a high-dielectric material facing the radiation conductor plate;
  • a microstrip antenna comprising: A microstrip antenna is provided, wherein the high dielectric is composed of the dielectric substrate.
  • thermosetting resin composition excellent in void suppression and filling properties during molding of a member, shape retention property, toughness, high dielectric constant and low dielectric loss tangent in the member, and use thereof It is possible to provide a high-frequency device that Further, according to the second invention, a thermosetting resin composition from which a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent can be obtained, a dielectric substrate made of the resin composition, and the dielectric substrate are provided. A microstrip antenna can be provided.
  • FIG. 1 is a top perspective view showing a microstrip antenna of this embodiment
  • FIG. 4 is a cross-sectional view showing another aspect of the microstrip antenna of this embodiment
  • thermosetting resin composition of the first embodiment An outline of the thermosetting resin composition of the first embodiment will be described.
  • the thermosetting resin composition of the present embodiment contains an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C), and the high dielectric constant filler (C) is the thermosetting resin composition 50% by mass or more of calcium titanate particles or 60% by mass or more of strontium titanate particles in 100% by mass of the solid content of the product,
  • the epoxy resin (A) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin
  • the curing agent (B) contains an active ester compound (B1) and/or a phenolic curing agent (B2), and an active ester
  • the compound is at least selected from an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, and an active ester compound containing a benzoylated phenol novolak.
  • thermosetting resin composition has a flexural modulus at 260° C. of 50 N/mm 2 or more and 190 N/mm 2 or less, measured according to procedure 1 below, and measured according to procedure 2 below.
  • the rectangular pressure is configured to be 0.2 MPa or more and 8.8 MPa or less.
  • thermosetting resin composition In response to the current demand for high dielectric constant and low dielectric loss tangent, it has become necessary to increase the content of specific high dielectric constant fillers. However, depending on the type and content of the high dielectric constant filler, the moldability of the thermosetting resin composition may deteriorate. In order to deal with such molding defects, the present inventors investigated the flow characteristics of thermosetting resin compositions. According to the findings of the present inventors, the rectangular pressure as an index can stably evaluate the flow characteristics of a thermosetting resin composition highly filled with a high dielectric constant filler. Therefore, a thermosetting resin composition having excellent moldability can be realized by setting the Kogeba viscosity to the above upper limit or less.
  • the temperature of the operating environment tends to increase more and more due to design circumstances such as higher frequency, higher output of power semiconductors, and lower profile of devices.
  • the inventors investigated the thermal properties of a cured product of a thermosetting resin composition.
  • the index of flexural modulus at 260° C. can stably evaluate the resistance to deformation of a cured product of a thermosetting resin composition under heat. Therefore, by setting the 260° C. flexural modulus to the above lower limit or higher, it can be expected that deterioration of the dielectric properties of the member due to thermal deterioration can be suppressed.
  • thermosetting resin composition for example, by appropriately selecting the type and amount of each component contained in the thermosetting resin composition, the method of preparing the thermosetting resin composition, etc., the above rectangular pressure, 260 ° C. bending It is possible to control the elastic modulus, 25° C. bending elastic modulus, 260° C. bending strength, 25° C. bending strength, water absorption, thermal conductivity, die shear strength, glass transition temperature, and linear expansion coefficient.
  • 50% by mass or more of calcium titanate particles or 60% by mass or more of strontium titanate particles are used as high dielectric constant fillers, and biphenyl aralkyl type epoxy resin and/or biphenyl type epoxy resin are used as epoxy resin.
  • the lower limit of the bending elastic modulus at 260°C is 50 N/mm 2 or more, preferably 60 N/mm 2 or more, more preferably 70 N/mm 2 or more. Thereby, the shape retainability of the member can be improved.
  • the upper limit of the bending elastic modulus at 260°C is 190 N/mm 2 or less, preferably 180 N/mm 2 or less, more preferably 150 N/mm 2 or less. Thereby, the toughness of the member can be improved.
  • the lower limit of the rectangular pressure is 0.2 MPa or higher, preferably 0.25 MPa or higher, and more preferably 0.3 MPa or higher. This can suppress the generation of voids during molding of the member.
  • the upper limit of the rectangular pressure is 8.8 MPa or less, preferably 8.7 MPa or less, more preferably 8.6 MPa or less. As a result, it is possible to improve filling properties during molding of the member.
  • the lower limit of the bending elastic modulus at 25°C is, for example, 9000 N/mm 2 or more, preferably 10000 N/mm 2 or more, more preferably 12000 N/mm 2 or more. Thereby, the shape retention of the member at room temperature can be improved.
  • the upper limit of the bending elastic modulus at 25°C is, for example, 28,000 N/mm 2 or less, preferably 27,000 N/mm 2 or less, and more preferably 26,000 N/mm 2 or less. This can improve the toughness of the member at room temperature.
  • the lower limit of the bending strength at 25°C is, for example, 40 N/mm 2 or more, preferably 45 N/mm 2 or more, more preferably 50 N/mm 2 or more. Thereby, the shape retention of the member at room temperature can be improved.
  • the upper limit of the bending strength at 25°C is, for example, 200 N/mm 2 or less, preferably 180 N/mm 2 or less, more preferably 150 N/mm 2 or less. This can improve the toughness of the member at room temperature.
  • the lower limit of the bending strength at 260°C is, for example, 0.1 N/mm 2 or more, preferably 0.5 N/mm 2 or more, and more preferably 1 N/mm 2 or more. Thereby, the shape retention of the member can be improved in a high-temperature environment.
  • the upper limit of bending strength at 260°C is, for example, 10 N/mm 2 or less, preferably 7 N/mm 2 or less, and more preferably 5 N/mm 2 or less. This can improve the toughness of the member in a high-temperature environment.
  • the lower limit of water absorption is not particularly limited, it may be 0.01% or more and 0.05% or more.
  • the upper limit of water absorption is, for example, 0.8% or less, preferably 0.7% or less, and more preferably 0.6% or less. Thereby, low water absorption of the member can be achieved.
  • the lower limit of thermal conductivity is, for example, 1.0 W/mK or higher, preferably 1.5 W/mK or higher, and more preferably 2.0 W/mK or higher. Thereby, the heat transfer characteristics of the member can be improved.
  • the upper limit of the thermal conductivity is not particularly limited, it may be 5.0 W/mK or less, preferably 4.0 W/mK or less.
  • the lower limit of die shear strength to copper is, for example, 5 N/mm 2 or more, preferably 6 N/mm 2 or more, more preferably 7 N/mm 2 or more. Thereby, the adhesion with the metal member can be improved.
  • the upper limit of the die shear strength to copper is not particularly limited, but may be 50 N/mm 2 or less, 40 N/mm 2 or less, or 30 N/mm 2 or less.
  • the lower limit of the glass transition temperature is, for example, 90°C or higher, preferably 95°C or higher, more preferably 100°C or higher. Thereby, the heat resistance of the member can be improved.
  • the upper limit of the glass transition temperature is not particularly limited, it may be 200° C. or lower and 190° C. or lower.
  • CTE1 is the coefficient of linear expansion in the range below the glass transition temperature
  • CTE2 is the coefficient of linear expansion in the range above the glass transition temperature to 320°C or less.
  • CTE1 is not particularly limited, it may be 5 ppm/°C or higher and 6 ppm/°C or higher.
  • the upper limit of CTE1 is, for example, 30 ppm/°C or less, preferably 28 ppm/°C or less, more preferably 25 ppm or less. Thereby, the dimensional change of the member below Tg can be suppressed.
  • the lower limit of CTE2 is not particularly limited, but may be 10 ppm/°C or higher, preferably 30 ppm/°C or higher.
  • the upper limit of CTE2 is, for example, 100 ppm/°C or less, preferably 90 ppm/°C or less, more preferably 80 ppm/°C or less. Thereby, it is possible to suppress the dimensional change of the member when it is heated.
  • thermosetting resin composition is injection molded into a mold using a low-pressure transfer molding machine under the conditions of a mold temperature of 130 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. A molding of 80 mm is obtained. The resulting molded article is post-cured at 175° C. for 4 hours to prepare a test piece.
  • the flexural modulus (N/mm 2 ) and flexural strength (N/mm 2 ) of the test piece were measured at a head speed of 5 mm/min and at room temperature (25°C) and 260°C. Measure.
  • thermosetting resin composition was injected into a rectangular flow path with a width of 13 mm, a thickness of 1 mm, and a length of 175 mm under conditions of a mold temperature of 175°C and an injection speed of 177 mm 3 /sec. did.
  • a pressure sensor embedded at a position 25 mm from the upstream end of the flow channel measures the change in pressure over time, measures the minimum pressure (MPa) when the thermosetting resin composition flows, and presses this into a rectangle. .
  • thermosetting resin composition is molded under the conditions of a mold temperature of 175 ° C., an injection pressure of 10 MPa, and a curing time of 180 seconds. Mold 4 pieces per level. Subsequently, using an automatic die shear measuring device, the die shear strength between the test piece and the copper lead frame is measured at room temperature. The die shear strength of four specimens is taken.
  • thermosetting resin composition of this embodiment will be described in detail below.
  • thermosetting resin composition of this embodiment contains an epoxy resin (A) as a thermosetting resin.
  • Epoxy resin (A) can be any monomer, oligomer, or polymer having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not limited.
  • the epoxy resin (A) contains at least a biphenylaralkyl-type epoxy resin and/or a biphenyl-type epoxy resin (excluding a biphenylaralkyl-type epoxy resin).
  • the epoxy resin (A) may contain epoxy resins other than the biphenyl aralkyl type epoxy resin and the biphenyl type epoxy resin.
  • the biphenyl aralkyl type epoxy resin include a phenol aralkyl type epoxy resin having a biphenylene skeleton, a naphthol aralkyl type epoxy resin having a biphenylene skeleton, and the like.
  • epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, and other bisphenol type epoxy resins; stilbene type epoxy resins; phenol novolac type epoxy resins and cresol novolak type epoxy resins.
  • Novolac type epoxy resins such as; triphenol methane type epoxy resins, polyfunctional epoxy resins such as trisphenol type epoxy resins exemplified by alkyl-modified triphenol methane type epoxy resins; phenol aralkyl type epoxy resins having a phenylene skeleton, phenylene Phenol aralkyl epoxy resins such as naphthol aralkyl epoxy resins having a skeleton; epoxy resins containing a biphenylene skeleton; naphthol epoxy resins such as dihydroxynaphthalene epoxy resins and epoxy resins obtained by glycidyl-etherifying dihydroxynaphthalene dimers triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as dicyclopentadiene-modified phenol type epoxy resins. These may be
  • thermosetting resin composition may contain thermosetting resins other than the epoxy resin.
  • thermosetting resins one or more selected from cyanate resins and maleimide resins may be included.
  • the content of the epoxy resin (A) is, for example, 5% by mass or more, preferably 7% by mass or more in 100% by mass of the thermosetting resin composition. Moreover, the content of the epoxy resin (A) is, for example, 20% by mass or less, preferably 15% by mass or less in 100% by mass of the thermosetting resin composition.
  • the thermosetting resin composition contains a high dielectric constant filler (high dielectric constant filler) (C).
  • the high dielectric constant filler (C) contains calcium titanate particles and/or strontium titanate particles. Thereby, the dielectric loss tangent in the high frequency band can be further reduced.
  • the thermosetting resin composition may contain high dielectric constant fillers other than calcium titanate particles and strontium titanate particles.
  • high dielectric constant fillers include magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium zirconate titanate, lead zirconate titanate, niobium barium magnesium acid, calcium zirconate, and the like. One or two or more selected from these can be used.
  • D 10 is the particle diameter at which the cumulative value is 10%
  • D 50 is the particle diameter at which the cumulative value is 50%
  • the cumulative The particle diameter at which the value is 90 % is defined as D90.
  • D 10 , D 50 and D 90 are, for example, 0.25 ⁇ (D 90 ⁇ D 10 )/D 50 ⁇ 55, preferably 0.5 ⁇ (D 90 ⁇ D 10 )/D 50 ⁇ 50, more preferably is configured to satisfy 1.0 ⁇ (D 90 ⁇ D 10 )/D 50 ⁇ 40.
  • D50 is, for example, preferably 0.1 ⁇ m or more and 50 ⁇ m or less, more preferably 0.3 ⁇ m or more and 20 ⁇ m or less, still more preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the shape of the high dielectric constant filler (C) is granular, amorphous, flaky, etc., and the high dielectric constant filler (C) in these shapes can be used at any ratio.
  • the lower limit of the content of calcium titanate particles is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more in 100% by mass of the thermosetting resin composition. Thereby, the dielectric loss tangent in the high frequency band can be further reduced.
  • the lower limit of the strontium titanate particles is 60% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more in 100% by mass of the thermosetting resin composition. Thereby, the dielectric loss tangent in the high frequency band can be further reduced.
  • the upper limit of calcium titanate particles and/or strontium titanate particles is, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less in 100% by mass of the thermosetting resin composition. Thereby, the production stability of the molded product can be improved.
  • the thermosetting resin composition contains a curing agent (B).
  • the curing agent contains an active ester compound (B1) and/or a phenolic curing agent (B2).
  • the curing agent contains an active ester compound (B1) and a phenolic curing agent (B2).
  • the active ester compound (B1) functions as a curing agent for thermosetting resins such as epoxy resins.
  • the active ester compound (B1) includes an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, and an active ester compound containing a benzoylated phenol novolac. Including one or more selected from the group consisting of Among these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable.
  • "Dicyclopentadiene-type diphenol structure” represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
  • the active ester compound (B1) for example, a resin having a structure represented by the following general formula (1) can be used.
  • A is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group
  • Ar' is a substituted or unsubstituted aryl group
  • B is a structure represented by the following general formula (B), k is the average value of repeating units and ranges from 0.25 to 3.5.
  • Ar is a substituted or unsubstituted arylene group.
  • Substituents of the substituted arylene group include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, phenyl groups and aralkyl groups.
  • Y is a single bond, a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, or a substituted or unsubstituted divalent is an aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group.
  • Substituents for the aforementioned groups include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, phenyl groups, aralkyl groups and the like.
  • Y include a single bond, a methylene group, —CH(CH 3 ) 2 —, an ether bond, an optionally substituted cycloalkylene group, an optionally substituted 9,9-fluorenylene group, and the like.
  • n is an integer of 0-4, preferably 0 or 1;
  • B is a structure represented by the following general formula (B1) or the following general formula (B2).
  • the resulting cured product can have excellent dielectric properties and excellent low dielectric loss tangent.
  • the active ester compound (B1) used in the thermosetting resin composition of this embodiment has an active ester group represented by formula (B).
  • the active ester group of the active ester compound (B1) reacts with the epoxy group of the epoxy resin (A) to generate secondary hydroxyl groups. This secondary hydroxyl group is blocked by an ester residue of the active ester compound (B1). Therefore, the dielectric loss tangent of the cured product is reduced.
  • the structure represented by formula (B) above is preferably at least one selected from the following formulas (B-1) to (B-6).
  • each R 1 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group;
  • Each R 2 is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group
  • X is a linear alkylene group having 2 to 6 carbon atoms, ether a bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group
  • n is an integer of 0-4
  • p is an integer of 1-4.
  • thermosetting A cured product of the flexible resin composition has a low dielectric loss tangent in a high frequency band.
  • an active ester compound having a structure represented by formula (B-2), formula (B-3) or formula (B-5) is preferable, and furthermore, the active ester compound of formula (B-2)
  • An active ester compound having a structure in which n is 0, a structure in which X in formula (B-3) is an ether bond, or a structure in which two carbonyloxy groups are at the 4,4'-positions in formula (B-5) is more preferred.
  • all R 1 in each formula are preferably hydrogen atoms.
  • Ar′ in formula (1) is an aryl group, such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 3,5-xylyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 2-benzylphenyl group, 4-benzylphenyl group, 4-( ⁇ -cumyl)phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
  • a 1-naphthyl group or a 2-naphthyl group is preferable because a cured product having a particularly low dielectric loss tangent can be obtained.
  • [A] in the active ester compound (B1) represented by formula (1) is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group.
  • the arylene group includes, for example, a structure obtained by polyaddition reaction of an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule and a phenolic compound.
  • the unsaturated aliphatic cyclic hydrocarbon compounds containing two double bonds in one molecule are, for example, dicyclopentadiene, cyclopentadiene oligomers, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene. , limonene, etc., and these may be used alone or in combination of two or more.
  • dicyclopentadiene is preferable because a cured product having excellent heat resistance can be obtained.
  • dicyclopentadiene is contained in petroleum distillates, industrial dicyclopentadiene may contain cyclopentadiene polymers and other aliphatic or aromatic diene compounds as impurities.
  • the phenolic compounds include, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like, each alone You may use and you may use two or more types together. Among these, phenol is preferable because it has high curability and becomes an active ester compound having excellent dielectric properties in a cured product.
  • [A] in the active ester compound represented by formula (1) has a structure represented by formula (A).
  • a cured product of a thermosetting resin composition containing an active ester compound in which [A] in formula (1) has the following structure can achieve a low dielectric loss tangent in a high frequency band.
  • each R 3 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; l is 0 or 1, and m is an integer of 1 or more.
  • active ester curing agents represented by formula (1) more preferable ones include resins represented by the following formulas (1-1), (1-2) and (1-3), Especially preferred are resins represented by the following formula (1-3).
  • R 1 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group.
  • Z is a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus
  • l is 0 or 1
  • k is a repeating unit is the average of 0.25 to 3.5.
  • R 1 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group.
  • Z is a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus
  • l is 0 or 1
  • k is a repeating unit is the average of 0.25 to 3.5.
  • R 1 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group.
  • Z is a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus
  • l is 0 or 1
  • k is a repeating unit is the average of 0.25 to 3.5.
  • the active ester compound (B1) represented by the general formula (A) is a phenolic compound (a) having a structure in which a plurality of aryl groups having a phenolic hydroxyl group are connected via an aliphatic cyclic hydrocarbon group, It can be produced by a known method of reacting an aromatic nucleus-containing dicarboxylic acid or its halide (b) with an aromatic monohydroxy compound (c).
  • the reaction ratio of the phenolic compound (a), the aromatic nucleus-containing dicarboxylic acid or its halide (b), and the aromatic monohydroxy compound (c) can be appropriately adjusted according to the desired molecular design.
  • the phenolic compound Ratio of 0.25 to 0.90 moles of phenolic hydroxyl groups possessed by (a) and 0.10 to 0.75 moles of hydroxyl groups possessed by the aromatic monohydroxy compound (c) It is preferable to use each raw material in, the phenolic hydroxyl group of the phenolic compound (a) is in the range of 0.50 to 0.75 mol, and the hydroxyl group of the aromatic monohydroxy compound (c) is It is more preferable to use each raw material in a ratio within the range of 0.25 to 0.50 mol.
  • the functional group equivalent of the active ester compound (B1) is a cured product with excellent curability and low dielectric loss tangent when the total number of functional groups of the resin is the arylcarbonyloxy group and phenolic hydroxyl group in the resin structure. 200 g/eq or more and 230 g/eq or less, more preferably 210 g/eq or more and 220 g/eq or less.
  • the content of the active ester compound (B1) and the epoxy resin (A) is excellent in curability, and a cured product with a low dielectric loss tangent can be obtained. It is preferable that the ratio of the epoxy groups in the epoxy resin (A) is 0.8 to 1.2 equivalents with respect to the total equivalent of the active groups in (B1).
  • the active group in the active ester compound (B1) refers to an arylcarbonyloxy group and a phenolic hydroxyl group in the resin structure.
  • the active ester compound (B1) is preferably 0.5% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 12% by mass or less, still more preferably 2% by mass in 100% by mass of the thermosetting resin composition. It is used in an amount of 9% by mass or more.
  • the obtained cured product can have more excellent dielectric properties and is further excellent in low dielectric loss tangent.
  • thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent by using the active ester compound (B1) and the high dielectric constant filler (C) in combination, and is also excellent in these effects.
  • the active ester compound (B1) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass, with respect to 100 parts by mass of the high dielectric constant filler (C). parts or less, more preferably 3 parts by mass or more and 15 parts by mass or less.
  • the phenol-based curing agent (B2) functions as a curing agent for thermosetting resins such as epoxy resin (A).
  • the phenolic curing agent (B2) contains a biphenylaralkyl-type phenolic resin and/or a phenolic novolak resin.
  • the thermosetting resin composition may contain a curing agent other than the biphenylaralkyl-type phenolic resin and the phenolic novolac resin.
  • a curing agent other than the biphenylaralkyl-type phenolic resin and the phenolic novolac resin examples include phenol aralkyl resins containing a biphenylene skeleton, naphthol aralkyl resins containing a biphenylene skeleton, and the like.
  • the thermosetting resin composition of this embodiment can contain a curing agent other than the active ester compound (B1).
  • Other curing agents include phenolic resin curing agents other than biphenylaralkyl type phenolic resins and phenolic novolac resins, amine compound curing agents, amide compound curing agents, acid anhydride curing agents, and the like. These may be used alone or in combination of two or more. Among these, a phenolic resin curing agent may be used.
  • Phenolic resin-based curing agents include, for example, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol addition type resins, phenolic resins containing a biphenylene skeleton, trimethylolmethane resins, tetraphenylolethane resins, and naphthols.
  • Novolak resin Novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl-modified naphthol resin (phenol nucleus is linked by bismethylene group)
  • Polyhydric phenol compounds such as linked polyhydric naphthol compounds
  • aminotriazine-modified phenol resins polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.
  • Amine compound curing agents include, for example, amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complexes and guanidine derivatives.
  • amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complexes and guanidine derivatives.
  • amide compound-based curing agents include polyamide resins synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine.
  • Acid anhydride curing agents include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride may be mentioned.
  • the amount of the phenolic curing agent (B2) is preferably 0.5% by mass or more and 15% by mass or less, more preferably 100% by mass of the thermosetting resin.
  • the amount is 1% by mass or more and 10% by mass or less.
  • the thermosetting resin composition may contain a curing catalyst.
  • a curing catalyst may also be called a curing accelerator or the like.
  • the curing catalyst is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and known curing catalysts can be used.
  • phosphorus atom-containing compounds such as organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 2-methylimidazole, 2- imidazoles such as phenylimidazole (imidazole-based curing accelerators); Nitrogen atom-containing compounds such as salts can be mentioned, and only one type may be used, or two or more types may be used.
  • a phosphorus atom-containing compound such as a tetra-substituted phosphonium compound, a phosphobetaine compound, a phosphine compound and a quinone compound. It is more preferable to include latent compounds such as adducts of phosphonium compounds and silane compounds, tetrasubstituted phosphonium compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Adducts are particularly preferred.
  • organic phosphines examples include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.
  • thermosetting resin composition When a curing catalyst is used, its content is preferably 0.05 to 3% by mass, more preferably 0.08 to 2% by mass, based on 100% by mass of the thermosetting resin composition. By setting it to such a numerical range, a sufficient curing acceleration effect can be obtained without excessively deteriorating other performances.
  • thermosetting resin composition of the present embodiment may further contain an inorganic filler in addition to the high dielectric constant filler (C) in order to reduce hygroscopicity, reduce the coefficient of linear expansion, improve thermal conductivity and improve strength. can.
  • Inorganic fillers include fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, Examples include powders of mullite, titania, etc., beads obtained by spheroidizing these powders, glass fibers, and the like. These inorganic fillers may be used alone or in combination of two or more. Among the above inorganic fillers, silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. preferable.
  • the content of the inorganic filler other than the high dielectric constant filler (C) is preferably 3 in the solid content of 100% by mass of the thermosetting resin composition, from the viewpoint of moldability, reduction of thermal expansion, and improvement of strength. It can be in the range of 5% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less. If it is the said range, it will be excellent in thermal-expansion reduction and moldability.
  • the content of silica may be, for example, 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less in 100% by mass of the solid content of the thermosetting resin composition.
  • the content of the aluminum-based substrate may be, for example, 40% by mass or less, preferably 38% by mass or less, more preferably 35% by mass or less in 100% by mass of the solid content of the thermosetting resin composition.
  • thermosetting resin composition of the present embodiment may optionally contain various components such as a silane coupling agent, a release agent, an adhesion aid, a colorant, a dispersant, and a stress reducing agent.
  • a silane coupling agent such as silane coupling agent, a release agent, an adhesion aid, a colorant, a dispersant, and a stress reducing agent.
  • thermosetting resin composition of this embodiment can be produced by uniformly mixing the components described above.
  • the production method include a method of sufficiently mixing raw materials in a predetermined content with a mixer or the like, melt-kneading the mixture with a mixing roll, a kneader, an extruder or the like, and then cooling and pulverizing the mixture.
  • the resulting thermosetting resin composition may, if desired, be tableted to a size and mass that are suitable for molding conditions.
  • thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent in the high frequency band. can be planned.
  • thermosetting resin composition can be used to form part of a high frequency device selected from the group consisting of microstrip antennas, dielectric waveguides, and multilayer antennas.
  • the high-frequency device of this embodiment includes a cured product obtained from a thermosetting resin composition.
  • a thermosetting resin composition An example of a high frequency device will be described below.
  • a microstrip antenna 10 includes a dielectric substrate 12 obtained by curing the thermosetting resin composition described above, and a radiation conductor plate (radiation element) provided on one surface of the dielectric substrate 12. ) 14 and a ground conductor plate 16 provided on the other surface of the dielectric substrate 12 .
  • the shape of the radiation conductor plate can be rectangular or circular. In this embodiment, an example using a rectangular radiation conductor plate 14 will be described.
  • the radiation conductor plate 14 includes any one of a metal material, an alloy of metal materials, a hardened metal paste, and a conductive polymer.
  • Metallic materials include copper, silver, palladium, gold, platinum, aluminum, chromium, nickel, cadmium lead, selenium, manganese, tin, vanadium, lithium, cobalt, titanium, and the like.
  • An alloy includes multiple metallic materials.
  • the metal paste contains powder of a metal material kneaded with an organic solvent and a binder. Binders include epoxy resins, polyester resins, polyimide resins, polyamideimide resins, and polyetherimide resins.
  • Conductive polymers include polythiophene-based polymers, polyacetylene-based polymers, polyaniline-based polymers, polypyrrole-based polymers, and the like.
  • the microstrip antenna 10 of this embodiment has a radiation conductor plate 14 having a length L and a width W, and resonates at a frequency where L is an integer multiple of 1/2 wavelength.
  • L is an integer multiple of 1/2 wavelength.
  • the thickness h of the dielectric substrate 12 and the width W of the radiation conductor plate 14 are designed to be sufficiently small with respect to the wavelength.
  • the ground conductor plate 16 is a thin plate made of highly conductive metal such as copper, silver, and gold.
  • the thickness is sufficiently thin with respect to the central operating frequency of the antenna device, and may be about 1/50 to 1/1000 wavelength of the central operating frequency.
  • feeding methods for microstrip antennas include direct feeding methods such as rear coaxial feeding and coplanar feeding, and electromagnetic coupling feeding methods such as slot coupling feeding and proximity coupling feeding.
  • power can be fed from the back of the antenna to the radiating conductor plate 14 by using a coaxial line or connector passing through the ground conductor plate 16 and the dielectric substrate 12 .
  • the radiation conductor plate 14 can be fed with a microstrip line (not shown) arranged on the same plane as the radiation conductor plate 14 .
  • another dielectric substrate (not shown) is provided so as to sandwich the ground conductor plate 16, and the radiation conductor plate 14 and the microstrip line are formed on separate dielectric substrates.
  • the radiation conductor plate 14 is excited by electromagnetically coupling the radiation conductor plate 14 and the microstrip line through a slot formed in the ground conductor plate 16 .
  • the dielectric substrate 12 has a laminated structure, and the dielectric substrate on which the radiation conductor plate 14 is formed and the dielectric substrate on which the strip conductor of the microstrip line and the ground conductor plate 16 are arranged. It is layered.
  • the radiation conductor plate 14 is excited by extending the strip conductor of the microstrip line below the radiation conductor plate 14 and electromagnetically coupling the radiation conductor plate 14 and the microstrip line.
  • the microstrip antenna 20 includes a dielectric substrate 22, a radiation conductor plate 14 provided on one surface of the dielectric substrate 22, and a radiation conductor plate 14 provided on the other surface of the dielectric substrate 22. and a high dielectric substrate (high dielectric) 24 facing the radiation conductor plate 14 .
  • the dielectric substrate 22 and the radiation conductor plate 14 and the high dielectric substrate 24 can be configured to be separated from each other by a predetermined distance with spacers 26 interposed therebetween.
  • the dielectric substrate 22 is composed of a substrate having a low dielectric constant such as a Teflon substrate.
  • the high dielectric substrate 24 is composed of a dielectric substrate obtained by curing the resin composition described above.
  • the gap between the dielectric substrate 22 and the high dielectric substrate 24 may be a space or may be filled with a dielectric material.
  • a structure in which a high dielectric substrate 24 is brought into contact with the upper surface of the radiation conductor plate 14 can be employed.
  • the dielectric waveguide comprises a dielectric obtained by curing the thermosetting resin composition of this embodiment, and a conductor film covering the surface of the dielectric.
  • a dielectric waveguide confines electromagnetic waves in a dielectric (dielectric medium) for transmission.
  • the conductor film can be made of a metal such as copper, an oxide high-temperature superconductor, or the like.
  • the multilayer antenna comprises a dielectric sheet obtained by curing the thermosetting resin composition of this embodiment.
  • a multi-layer antenna is a module obtained by printing a circuit consisting of a large number of elements such as capacitors and inductors on dielectric sheets and stacking them.
  • thermosetting resin composition of the second embodiment contains an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C). Each component is described below.
  • Epoxy resin (A) examples include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, glycidylamine-type epoxy resin, and naphthol aralkyl-type epoxy resin. and at least one selected from these.
  • the epoxy resin (A) is preferably a naphthol aralkyl type epoxy resin or a dicyclopentadiene type epoxy resin, more preferably a naphthol aralkyl type epoxy resin, from the viewpoint of the effects of the present invention.
  • the epoxy resin (A) can contain a combination of other epoxy resins, such as a biphenyl aralkyl type epoxy resin.
  • the epoxy resin (A) can be contained in an amount of 5% by mass or more and 20% by mass or less, preferably 10% by mass or more and 15% by mass or less with respect to the entire thermosetting resin composition.
  • the curing agent (B) contains an active ester curing agent (B1) and/or a phenolic curing agent (B2).
  • active ester curing agent (B1)) As the active ester curing agent (active ester compound) (B1), a compound having one or more active ester groups in one molecule can be used. Among them, the active ester curing agent (B1) contains an ester group with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having two or more are preferred.
  • a combination of the specific epoxy resin (A) described above and an active ester-based curing agent (B1) as a curing agent (B) results in a dielectric resin excellent in high dielectric constant and low dielectric loss tangent.
  • a body substrate can be obtained.
  • the same active ester compound as described in the embodiment of the first invention can be used.
  • the active ester curing agent (B1) used in the present invention includes a phenolic compound (a) having a structure in which a plurality of aryl groups having a phenolic hydroxyl group are knotted via an aliphatic cyclic hydrocarbon group, and an aromatic nucleus-containing It can be produced by a known method of reacting a dicarboxylic acid or its halide (b) with an aromatic monohydroxy compound (c).
  • the reaction ratio of the phenolic compound (a), the aromatic nucleus-containing dicarboxylic acid or its halide (b), and the aromatic monohydroxy compound (c) can be appropriately adjusted according to the desired molecular design. Among them, since an active ester-based curing agent (B1) with higher curability can be obtained, the phenol The phenolic hydroxyl group possessed by the aromatic compound (a) is in the range of 0.25 to 0.90 mol, and the hydroxyl group possessed by the aromatic monohydroxy compound (c) is in the range of 0.10 to 0.75 mol.
  • each raw material in such a ratio that the phenolic hydroxyl group of the phenolic compound (a) is in the range of 0.50 to 0.75 mol, and the hydroxyl of the aromatic monohydroxy compound (c) is It is more preferable to use each raw material in a proportion that results in a range of 0.25 to 0.50 mol of groups.
  • the functional group equivalent of the active ester curing agent (B1) is excellent in curability and curing with a low dielectric loss tangent when the sum of the arylcarbonyloxy groups and phenolic hydroxyl groups in the resin structure is taken as the total number of functional groups in the resin. 200 g/eq or more and 230 g/eq or less, more preferably 210 g/eq or more and 220 g/eq or less.
  • the blending amount of the active ester curing agent (B1) and the epoxy resin (A) is excellent in curability, and a cured product with a low dielectric loss tangent can be obtained. It is preferable that the amount of epoxy groups in the epoxy resin (A) is 0.8 to 1.2 equivalents per equivalent of the total active groups in the ester curing agent (B1).
  • the active group in the active ester curing agent (B1) refers to an arylcarbonyloxy group and a phenolic hydroxyl group in the resin structure.
  • the active ester curing agent (B1) is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass, based on the total thermosetting resin composition. It is used in an amount of 10 mass % or more, more preferably 1.0 mass % or more and 7 mass % or less.
  • the obtained cured product can have more excellent dielectric properties, and is further excellent in low dielectric loss tangent.
  • the resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent by using a combination of the active ester curing agent (B1) and the high dielectric constant filler (C) described later, and is also excellent in these effects.
  • the active ester curing agent (B1) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass, with respect to 100 parts by mass of the high dielectric constant filler (C) described later. 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less.
  • the applicant of the present invention uses a resin composition containing an epoxy resin and a predetermined active ester-based curing agent in a semiconductor encapsulation application different from the present invention.
  • the present invention differs from the technique described in the publication in that it contains a high dielectric constant filler.
  • the effect of the combination of the active ester curing agent and the epoxy resin is different in that it has a high dielectric constant and is excellent in high dielectric constant and low dielectric loss tangent in the high frequency band. is doing.
  • phenol-based curing agent (B2) examples include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, tetra Phenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl-modified naphthol resin ( polyhydric phenol compounds such as polyhydric naphthol compounds in which phenol nuclei are linked by bismethylene groups) and aminotriazine-modified phenol resins (polyhydric phenol compounds in which
  • the blending amount of the phenol-based curing agent (B2) is preferably 20% by mass or more and 70% by mass or less with respect to the epoxy resin (A). By using the curing agent in an amount within the above range, a resin composition having excellent curability can be obtained.
  • the ratio of the content of the phenolic curing agent b to the active ester curing agent a is preferably 0.5 or more and 8 or less, more preferably 1 or more and 5 or less, and still more preferably 1.5 or more and 3 or less.
  • the curing agent (B) containing the active ester curing agent (B1) and/or the phenolic curing agent (B2) is preferably 0.00 to the entire thermosetting resin composition. It is used in an amount of 2% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and still more preferably 1.0% by mass or more and 7% by mass or less.
  • the obtained cured product can have more excellent dielectric properties and is further excellent in low dielectric loss tangent.
  • the high dielectric constant filler (high dielectric constant filler) (C) includes calcium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, Zinc titanate, barium zirconate, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, calcium zirconate and the like can be mentioned, and at least one selected from these can be included.
  • the high dielectric constant filler (C) is preferably at least one selected from calcium titanate, strontium titanate, and magnesium titanate. Magnesium is more preferred.
  • the shape of the high dielectric constant filler (C) is granular, amorphous, flaky, etc., and these shapes of the high dielectric constant filler (C) can be used at any ratio.
  • the average particle size of the high dielectric constant filler (C) is preferably 0.1 ⁇ m or more and 50 ⁇ m or less, more preferably 0.3 ⁇ m or more and 20 ⁇ m or less, and further preferably It is preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the amount of the high dielectric constant filler (C) is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more in 100% by mass of the thermosetting resin composition. be.
  • the upper limit is about 80% by mass or more.
  • thermosetting resin composition of this embodiment can further contain a curing catalyst.
  • a curing catalyst may also be called a curing accelerator or the like.
  • the curing catalyst is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and known curing catalysts can be used.
  • phosphorus atom-containing compounds such as organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 2-methylimidazole, 2- imidazoles such as phenylimidazole (imidazole-based curing accelerators); Nitrogen atom-containing compounds such as salts can be mentioned, and only one type may be used, or two or more types may be used.
  • a phosphorus atom-containing compound such as a tetra-substituted phosphonium compound, a phosphobetaine compound, a phosphine compound and a quinone compound. It is more preferable to include latent compounds such as adducts of phosphonium compounds and silane compounds, tetrasubstituted phosphonium compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Adducts are particularly preferred.
  • organic phosphines include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.
  • Examples of tetra-substituted phosphonium compounds include compounds represented by the following general formula (6).
  • P represents a phosphorus atom.
  • R 4 , R 5 , R 6 and R 7 each independently represent an aromatic group or an alkyl group.
  • A represents an anion of an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group and a thiol group on an aromatic ring.
  • AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group and a thiol group on an aromatic ring.
  • x and y are 1 to 3
  • z is 0 to 3
  • x y.
  • a compound represented by the general formula (6) is obtained, for example, as follows. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and uniformly mixed to generate an aromatic organic acid anion in the solution system. Water is then added to precipitate the compound represented by general formula (6).
  • R 4 , R 5 , R 6 and R 7 bonded to the phosphorus atom are phenyl groups
  • AH is a compound having a hydroxyl group in the aromatic ring, that is, a phenol.
  • A is preferably the anion of the phenol.
  • phenols examples include monocyclic phenols such as phenol, cresol, resorcin and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene and anthraquinol; bisphenols such as bisphenol A, bisphenol F and bisphenol S; Examples include polycyclic phenols such as phenylphenol and biphenol.
  • Examples of phosphobetaine compounds include compounds represented by the following general formula (7).
  • P represents a phosphorus atom.
  • R 8 represents an alkyl group having 1 to 3 carbon atoms, and R 9 represents a hydroxyl group.
  • f is 0-5 and g is 0-3.
  • a compound represented by the general formula (7) is obtained, for example, as follows. First, the triaromatic-substituted phosphine, which is the third phosphine, is brought into contact with a diazonium salt to substitute the diazonium group of the triaromatic-substituted phosphine with the diazonium salt.
  • Examples of adducts of phosphine compounds and quinone compounds include compounds represented by the following general formula (8).
  • P represents a phosphorus atom.
  • R 10 , R 11 and R 12 each represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms and may be the same or different.
  • R 13 , R 14 and R 15 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different, and R 14 and R 15 combine to form a cyclic structure.
  • the phosphine compound used for the adduct of the phosphine compound and the quinone compound includes, for example, triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trinaphthylphosphine, tris(benzyl)phosphine and the like.
  • Substituents or those in which a substituent such as an alkyl group or an alkoxyl group is present are preferred, and examples of substituents such as an alkyl group or an alkoxyl group include those having 1 to 6 carbon atoms.
  • Triphenylphosphine is preferred from the viewpoint of availability.
  • the quinone compound used for the adduct of the phosphine compound and the quinone compound includes benzoquinone and anthraquinones, among which p-benzoquinone is preferable from the viewpoint of storage stability.
  • the adduct can be obtained by contacting and mixing in a solvent in which both the organic tertiary phosphine and the benzoquinones can be dissolved.
  • a solvent in which both the organic tertiary phosphine and the benzoquinones can be dissolved.
  • ketones such as acetone and methyl ethyl ketone, which have low solubility in the adduct, are preferred. However, it is not limited to this.
  • Examples of adducts of phosphonium compounds and silane compounds include compounds represented by the following general formula (9).
  • P represents a phosphorus atom and Si represents a silicon atom.
  • R 16 , R 17 , R 18 and R 19 each represent an aromatic or heterocyclic organic group or an aliphatic group, and may be the same or different.
  • R20 is an organic group that bonds with groups Y2 and Y3 .
  • R21 is an organic group that bonds with groups Y4 and Y5 .
  • Y2 and Y3 each represent a group formed by releasing protons from a proton - donating group , and the groups Y2 and Y3 in the same molecule combine with silicon atoms to form a chelate structure.
  • Y4 and Y5 represent a group formed by releasing protons from a proton - donating group, and the groups Y4 and Y5 in the same molecule bind to silicon atoms to form a chelate structure.
  • R 20 and R 21 may be the same or different, and Y 2 , Y 3 , Y 4 and Y 5 may be the same or different.
  • Z1 is an organic group having an aromatic or heterocyclic ring, or an aliphatic group.
  • R 16 , R 17 , R 18 and R 19 are, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group and methyl group. , ethyl group, n-butyl group, n-octyl group and cyclohexyl group. , an aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.
  • R20 is an organic group that bonds with Y2 and Y3 .
  • R 21 is an organic group that bonds with groups Y 4 and Y 5 .
  • Y2 and Y3 are groups formed by proton - releasing proton - donating groups , and the groups Y2 and Y3 in the same molecule bond with silicon atoms to form a chelate structure.
  • Y4 and Y5 are groups in which proton - donating groups release protons, and groups Y4 and Y5 in the same molecule bond with silicon atoms to form a chelate structure.
  • the groups R 20 and R 21 may be the same or different, and the groups Y 2 , Y 3 , Y 4 and Y5 may be the same or different.
  • the proton donor releases two protons
  • the proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, and furthermore, the adjacent carbon atoms constituting the aromatic ring have a carboxyl group or a hydroxyl group.
  • An aromatic compound having at least two hydroxyl groups is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbon atoms constituting an aromatic ring is more preferable.
  • examples include alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin, and among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferred.
  • Z 1 in general formula (9) represents an organic group or aliphatic group having an aromatic or heterocyclic ring, specific examples of which include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. and aliphatic hydrocarbon groups such as octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxy groups such as glycidyloxypropyl group, mercaptopropyl group, aminopropyl group, mercapto groups, alkyl groups having amino groups, and reactive substituents such as vinyl groups.
  • a method for producing an adduct of a phosphonium compound and a silane compound is, for example, as follows.
  • a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added and dissolved in a flask containing methanol, and then a sodium methoxide-methanol solution is added dropwise while stirring at room temperature. Furthermore, when a solution prepared in advance by dissolving a tetrasubstituted phosphonium halide such as tetraphenylphosphonium bromide in methanol is added dropwise thereto while stirring at room temperature, crystals are precipitated. Precipitated crystals are filtered, washed with water and dried in a vacuum to obtain an adduct of a phosphonium compound and a silane compound.
  • its content is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.8% by mass, relative to the entire resin composition.
  • thermosetting resin composition of the present embodiment further contains an inorganic filler in addition to the high dielectric constant filler (C) in order to reduce hygroscopicity, reduce the coefficient of linear expansion, improve thermal conductivity and improve strength. can be done.
  • Inorganic fillers include fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, Examples include powders of mullite, titania, etc., beads obtained by spheroidizing these powders, glass fibers, and the like. These inorganic fillers may be used alone or in combination of two or more. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. is preferred.
  • the amount of the inorganic filler other than the high dielectric constant filler (C) is preferably 15% by mass with respect to the entire thermosetting resin composition from the viewpoint of moldability, reduction of thermal expansion, and improvement of strength. Above, 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less. If it is the said range, it will be excellent in thermal-expansion reduction and moldability.
  • thermosetting resin composition of the present embodiment may optionally contain various components such as a silane coupling agent, a release agent, a colorant, a dispersant, and a stress reducing agent. can.
  • thermosetting resin composition can contain the following epoxy resin (A), the following curing agent (B), and the following high dielectric constant filler (C) in combination.
  • Epoxy resin (A) At least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, glycidylamine type epoxy resins, and naphthol aralkyl type epoxy resins.
  • it contains at least one selected from the group consisting of dicyclopentadiene type epoxy resins and naphthol aralkyl type epoxy resins. More preferably, it contains at least one selected from the group consisting of naphthol aralkyl type epoxy resins.
  • (Curing agent (B)) Contains an active ester curing agent (B1) and/or a phenolic curing agent (B2). It preferably contains an active ester curing agent (B1).
  • At least one selected from an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure is included. More preferably, it is an active ester curing agent having a structure represented by the general formula (1).
  • High dielectric constant filler (C) Calcium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium zirconate titanate, lead zirconate titanate, niobate It contains at least one selected from barium magnesiumate and calcium zirconate. Preferably, it contains at least one selected from calcium titanate, strontium titanate, and magnesium titanate. More preferably, it contains at least one selected from calcium titanate and magnesium titanate.
  • the epoxy resin (A), the curing agent (B) containing an active ester curing agent and/or a phenolic curing agent, and the high dielectric constant filler (C) are arbitrarily combined with each of the examples. be able to.
  • thermosetting resin composition of the present embodiment is
  • the epoxy resin (A) can be contained in an amount of preferably 5% by mass or more and 20% by mass or less, more preferably 10% by mass or more and 15% by mass or less, based on 100% by mass of the composition
  • Curing agent (B) in 100% by mass of the composition, preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, still more preferably 1.0% by mass % or more and 7% by mass or less
  • the high dielectric constant filler (C) can be contained in 100% by mass of the composition in an amount of preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.
  • the upper limit is 80% by mass.
  • the epoxy resin (A), the curing agent (B) containing an active ester curing agent, and the high dielectric constant filler (C) are combined to obtain a high dielectric constant and It is possible to provide a thermosetting resin composition from which a dielectric substrate having an excellent low dielectric loss tangent can be obtained.
  • thermosetting resin composition of this embodiment can be produced by uniformly mixing the components described above.
  • Examples of the production method include a method of sufficiently mixing raw materials in a predetermined amount with a mixer or the like, melt-kneading the mixture with a mixing roll, kneader, extruder or the like, and then cooling and pulverizing the mixture.
  • the resulting thermosetting resin composition may, if desired, be tableted to a size and mass that are suitable for molding conditions.
  • thermosetting resin composition of the present embodiment has a spiral flow length of 50 cm or more, preferably 55 cm or more, and more preferably 60 cm or more. Therefore, the thermosetting resin composition of this embodiment has excellent moldability.
  • a mold temperature of 175 ° C. is injected into a mold for spiral flow measurement according to EMMI-1-66. This can be done by injecting the resin molding material under conditions of a pressure of 6.9 MPa and a curing time of 120 seconds and measuring the flow length.
  • thermosetting resin composition of the present embodiment has a rectangular pressure of 0.1 MPa or more, preferably 0.15 MPa or more, more preferably 0.20 MPa or more, measured under the following conditions. Rectangular pressure is a parameter of melt viscosity, and the smaller the numerical value, the lower the melt viscosity.
  • the thermosetting resin composition of the present embodiment has a rectangular pressure within the above range, and is therefore excellent in mold filling properties during molding.
  • thermosetting resin composition was injected into a rectangular flow path with a width of 13 mm, a thickness of 1 mm, and a length of 175 mm under conditions of a mold temperature of 175°C and an injection speed of 177 mm 3 /sec. Then, the change in pressure over time is measured with a pressure sensor embedded at a position 25 mm from the upstream end of the flow channel, the minimum pressure at the time of flow of the thermosetting resin composition is calculated, and this minimum pressure is measured as a rectangular pressure.
  • the thermosetting resin composition of the present embodiment has the following dielectric constant and dielectric loss tangent (tan ⁇ ) in a cured product obtained by heating at 200° C. for 90 minutes.
  • the dielectric constant at 25 GHz by the cavity resonator method can be 10 or more, preferably 12 or more, more preferably 13 or more, and particularly preferably 14 or more.
  • the dielectric loss tangent (tan ⁇ ) at 25 GHz by the cavity resonator method can be 0.04 or less, preferably 0.03 or less, more preferably 0.02 or less, and particularly preferably 0.015 or less.
  • thermosetting resin composition of the present embodiment Since the cured product obtained from the thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent in the high frequency band, it is possible to increase the frequency and shorten the circuit and reduce the size of communication equipment. It can be suitably used as a material for forming a microstrip antenna, a material for forming a dielectric waveguide, a material for forming an electromagnetic wave absorber, and the like.
  • the dielectric waveguide comprises a dielectric obtained by curing the thermosetting resin composition of this embodiment, and a conductor film covering the surface of the dielectric.
  • a dielectric waveguide confines electromagnetic waves in a dielectric (dielectric medium) for transmission.
  • the conductor film can be made of a metal such as copper, an oxide high-temperature superconductor, or the like.
  • the electromagnetic wave absorber has a laminated structure of a support, a resistive film, a dielectric layer, and a reflective layer.
  • the electromagnetic wave absorber can be used as a ⁇ /4 type electromagnetic wave absorber having high electromagnetic wave absorption performance.
  • a resin base material etc. are mentioned as a support body.
  • the support can protect the resistive film and enhance the durability as a radio wave absorber.
  • Resistive films include indium tin oxide and molybdenum-containing resistive films.
  • the dielectric layer is formed by curing the thermosetting resin composition of this embodiment. Its thickness is about 10 ⁇ m or more and 2000 ⁇ m or less.
  • the reflective layer can function as a radio wave reflective layer, and includes, for example, a metal film.
  • Example A shows an example of the first invention (claims 1 to 14 and 23 to 25 at the time of filing) and the first embodiment.
  • Example B shows an example of the second invention (claims 15 to 22 and 23 to 25 at the time of filing) and the second embodiment.
  • thermosetting resin composition (Examples A1 to A19, Comparative Examples A1 to A4) ⁇ Preparation of thermosetting resin composition> The following raw materials were mixed at room temperature using a mixer at the contents shown in Table 1, and then roll-kneaded at 70 to 100°C. After cooling the obtained kneaded material, the kneaded material was pulverized to obtain a thermosetting resin composition in the form of powder particles. Then, a tablet-like thermosetting resin composition was obtained by tableting at high pressure.
  • Inorganic filler ⁇ Inorganic filler 1: fused spherical silica (average particle size: 31 ⁇ m) ⁇ Inorganic filler 2: fused spherical silica (average particle size: 0.6 ⁇ m) ⁇ Inorganic filler 3: alumina (average particle size: 0.6 ⁇ m) ⁇ Inorganic filler 4: alumina (average particle size: 30 ⁇ m)
  • D 10 is the particle diameter at which the cumulative value is 10%
  • D 50 is the particle diameter at which the cumulative value is 50%
  • D 90 is the particle diameter at which the value is 90%
  • D 10 is 0.7 ⁇ m
  • D 50 is 2.0 ⁇ m
  • D 90 is 7.5 ⁇ m
  • (D 90 ⁇ D 10 )/D 50 is 3.4. Met.
  • Epoxy resin 1 biphenyl aralkyl type epoxy resin (NC3000L, manufactured by Nippon Kayaku Co., Ltd.)
  • Epoxy resin 2 biphenyl type epoxy resin (YY-4000K, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin 3 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoate 2,3-epoxypropyl (manufactured by Nissan Chemical Industries, Ltd., FOLDI E101)
  • Epoxy resin 4 bisphenol fluorene epoxy resin (TBIS-GG, Taoka Chemical Co., Ltd.)
  • Epoxy resin 5 bisphenol fluorene epoxy resin (TBIS-RXG, Taoka Chemical Co., Ltd.)
  • Epoxy resin 6 dicyclopentadiene type epoxy resin (HP-7200L, manufactured by DIC)
  • Epoxy resin 7 branched alkyl chain epoxy resin (YL9057, Mitsubishi Chemical
  • Active ester compound 1 Active ester compound prepared by the following preparation method In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride ( Mole number of acid chloride group: 2.0 mol) and 1338 g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved.
  • Active ester compound 2 Active ester compound prepared by the following preparation method In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 203.0 g of 1,3-benzenedicarboxylic acid dichloride (acid chloride Mole number of group: 2.0 mol) and 1338 g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved.
  • the average value k of repeating units of the active ester resin was in the range of 0.5 to 1.0 as calculated from the reaction equivalent ratio.
  • the obtained active ester resin specifically had a structure represented by the following chemical formula. In the following formula, the average value k of repeating units was 0.5 to 1.0.
  • Phenolic curing agent 1 branched alkyl chain phenolic novolac resin (ST-007-02, manufactured by Meiwa Kasei Co., Ltd.)
  • Silane coupling agent - Silane coupling agent 1: phenylaminopropyltrimethoxysilane (CF4083, Dow Corning Toray Co., Ltd.) ⁇ Silane coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sila Ace, manufactured by JNC)
  • Coloring agent 1 Black titanium oxide (manufactured by Ako Kasei Co., Ltd.)
  • Releasing agent 1 Glycerin trimontanate (Rekolb WE-4, manufactured by Clariant Japan Co., Ltd.)
  • Stress reduction agent 1 Carboxyl group-terminated butadiene acrylic rubber (CTBN1008SP, manufactured by Ube Industries, Ltd.)
  • thermosetting resin composition was applied to a Si substrate and prebaked at 120° C. for 4 minutes to form a resin film having a coating thickness of 12 ⁇ m. This was heated in an oven at 200° C. for 90 minutes in a nitrogen atmosphere and hydrofluoric acid treatment (immersed in a 2 mass % hydrofluoric acid aqueous solution). After removing the substrate from the hydrofluoric acid, the cured film was peeled off from the Si substrate and used as a test piece.
  • a network analyzer HP8510C, a synthesized sweeper HP83651A, and a test set HP8517B were used as measuring devices. These devices and a cylindrical cavity resonator (inner diameter ⁇ 42 mm, height 30 mm) were set up. The resonance frequency, 3 dB bandwidth, transmitted power ratio, etc. were measured at a frequency of 18 GHz with and without inserting the test piece into the resonator. Then, by analytically calculating these measurement results with software, the dielectric properties such as dielectric constant (Dk) and dielectric loss tangent (Df) were determined.
  • the measurement mode was TE 011 mode.
  • the glass transition temperature (Tg) and linear expansion coefficients (CTE1, CTE2) of the cured product of the obtained thermosetting resin composition were measured as follows. First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), the thermosetting resin composition was injection molded at a mold temperature of 175° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. , 10 mm ⁇ 4 mm ⁇ 4 mm specimens were obtained. Then, after post-curing the obtained test piece at 175 ° C.
  • KTS-15 low-pressure transfer molding machine
  • thermomechanical analyzer manufactured by Seiko Electronics Industries Co., Ltd., TMA100
  • the measurement temperature range is 0 ° C. to 320 ° C.
  • the heating rate is Measurement was performed under the condition of 5°C/min. From these measurement results, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) were calculated.
  • thermosetting resin composition was cured using a low-pressure transfer molding machine ("KTS-30" manufactured by Kotaki Seiki Co., Ltd.) under the conditions of a mold temperature of 130 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. Injection molded into a mold. As a result, a molded article having a width of 10 mm, a thickness of 4 mm and a length of 80 mm was obtained. The resulting molded article was then post-cured at 175° C. for 4 hours. This produced a test piece for evaluation of mechanical strength.
  • KTS-30 low-pressure transfer molding machine
  • the flexural strength (N/mm 2 ) and flexural modulus (N/mm 2 ) of the test piece at room temperature (25° C.) or 260° C. were measured in accordance with JIS K 6911 at a head speed of 5 mm/min. did.
  • thermosetting resin composition was injected into the channel.
  • a pressure sensor embedded at a position of 25 mm from the upstream end of the flow channel measures the change in pressure over time, measures the minimum pressure (MPa) at the time of flow of the thermosetting resin composition, and calculates the rectangular pressure.
  • Rectangular pressure is a parameter of melt viscosity, and a smaller numerical value indicates a lower melt viscosity.
  • thermosetting resin composition (water absorption rate) Using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.), the thermosetting resin composition was injected and molded under the conditions of a mold temperature of 175 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. A test piece with a diameter of 50 mm and a thickness of 3 mm was prepared and post-cured at 175° C. for 4 hours. After that, the obtained test piece was humidified for 168 hours in an environment of 85° C. and 85% relative humidity, and the weight change before and after the humidification treatment was measured to obtain the moisture absorption rate. The unit is % (mass %).
  • thermo conductivity A molded product of 50 ⁇ 50 mm was measured at room temperature using a probe-type thermal conductivity measuring machine (manufactured by Showa Denko KK). The unit is W/m°C.
  • thermosetting resin composition was injection molded at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds.
  • a test piece of x4 mm x 4 mm was obtained.
  • the measurement temperature range is 0 ° C. to 320 ° C., and the heating rate is The dimensional change rate of the test piece was measured under the condition of 5°C/min. When the dimensional change rate of the test piece was 0.6% or less, the shape retention was evaluated as good ( ⁇ ), and when it exceeded 0.6%, it was evaluated as poor (x).
  • thermosetting resin composition was measured according to the KIc method specified in ASTM D5045-91.
  • Those having a fracture toughness value of 1.8 MPa ⁇ m 1/2 or more were evaluated as having good toughness ( ⁇ ), and those having less than 1.8 MPa ⁇ m 1/2 were evaluated as being poor (X).
  • thermosetting resin composition was injection molded at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds.
  • a test piece of x4 mm x 4 mm was obtained.
  • the cross section of the obtained test piece (molded article) was checked for the presence or absence of voids by SEM observation. A case where voids were not confirmed in the SEM image at five locations was evaluated as ⁇ , and a case where voids were confirmed at one or more of the five locations was evaluated as x.
  • Mold temperature 175 ° C.
  • injection speed 10.5 mm / s
  • injection pressure 3.5 MPa
  • curing time 120 seconds
  • tablet size 40 mm ⁇ -40 g (molding pressure 8 MPa).
  • a thermosetting resin was injected into a rectangular channel having a width of 5 mm and a slit gap (G) of 25 ⁇ m, and the filling length from the upstream end of the channel was measured.
  • the filling length was 8 mm or more, the filling property was evaluated as good ( ⁇ ), and when it was less than 8 mm, it was evaluated as poor.
  • thermosetting resin compositions of Examples A1 to A19 are superior to Comparative Examples A1 to A4 in high dielectric constant and low dielectric loss tangent in the high frequency band of the molded member, and compared to Comparative Example 3,
  • the shape retention of the member is excellent
  • the toughness of the member is excellent compared to Comparative Examples A1, A2, and A4, and the generation of voids during molding of the member is suppressed compared to Comparative Example A3.
  • the results showed excellent filling properties during molding of the member.
  • the thermosetting resin composition of each of these examples can be suitably used to form part of high-frequency devices such as microstrip antennas, dielectric waveguides, and multilayer antennas.
  • Example B> (Examples B1 to B17, Reference Example B1) The following raw materials were blended at room temperature using a mixer in the blending amounts shown in Table 3, and then roll-kneaded at 70 to 100°C. After cooling the obtained kneaded material, the kneaded material was pulverized to obtain a powdery resin composition. Subsequently, tablet-shaped resin composition was obtained by tablet-molding at high pressure.
  • Inorganic filler (Inorganic filler) ⁇ Inorganic filler 1: Fused spherical silica (manufactured by Denka Co., Ltd.)
  • High dielectric constant filler ⁇ High dielectric constant filler 1: calcium titanate (average particle size 2.0 ⁇ m) ⁇ High dielectric constant filler 2: Magnesium titanate (average particle size 0.8 ⁇ m, with surface treatment, manufactured by Titan Kogyo Co., Ltd.) ⁇ High dielectric constant filler 3: Strontium titanate (average particle size 1.6 ⁇ m)
  • Coloring agent Black titanium oxide (manufactured by Ako Kasei Co., Ltd.)
  • Coupling agent 1 phenylaminopropyltrimethoxysilane (CF4083, manufactured by Dow Corning Toray Co., Ltd.)
  • Coupling agent 2 3-mercaptopropyltrimethoxysilane (Sila Ace, manufactured by JNC)
  • Epoxy resin - Epoxy resin 1: biphenylene skeleton-containing phenol aralkyl type epoxy resin (NC3000L, manufactured by Nippon Kayaku Co., Ltd.)
  • Epoxy resin 2 naphthol aralkyl type epoxy resin (ESN-475V, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
  • Epoxy resin 3 bisphenol A type epoxy resin (YL6810, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin 4 bisphenol F type epoxy resin (jER806H, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin 5 phenol aralkyl type epoxy resin (Milex E-XLC-4L (epoxy equivalent weight 238 g / eq, softening point 62 ° C.), manufactured by Mitsui Chemicals)
  • Epoxy resin 6 naphthalene type epoxy resin (EPICLON HP-4770, manufactured by DIC Corporation)
  • Epoxy resin 7 dicyclopentadiene type
  • Curing agent 1 Active ester curing agent prepared by the following preparation method (Preparation method of active ester curing agent) 279.1 g of biphenyl-4,4′-dicarboxylic acid dichloride (moles of acid chloride group: 2.0 mol) and 1338 g of toluene were placed in a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer. was charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve.
  • ⁇ Curing agent 2 Active ester curing agent prepared by the following preparation method (Preparation method of active ester curing agent) A flask equipped with a thermometer, dropping funnel, condenser, fractionating tube and stirrer was charged with 203.0 g of 1,3-benzenedicarboxylic acid dichloride (moles of acid chloride group: 2.0 mol) and 1338 g of toluene. It was charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve.
  • the average value k of repeating units of the active ester resin was in the range of 0.5 to 1.0 as calculated from the reaction equivalent ratio.
  • the obtained active ester resin specifically had a structure represented by the following chemical formula. In the following formula, the average value k of repeating units was 0.5 to 1.0.
  • Silicone 1 dimethylsiloxane-diglycidin ether copolymer (M69B, manufactured by Sumitomo Bakelite Co., Ltd.)
  • a test piece was obtained using the resin composition. Specifically, the resin compositions prepared in Examples and Comparative Examples were applied to a Si substrate and prebaked at 120° C. for 4 minutes to form a resin film having a coating thickness of 12 ⁇ m. This was heated in an oven at 200° C. for 90 minutes in a nitrogen atmosphere and hydrofluoric acid treatment (immersed in a 2 mass % hydrofluoric acid aqueous solution). After removing the substrate from the hydrofluoric acid, the cured film was peeled off from the Si substrate and used as a test piece.
  • a network analyzer HP8510C, a synthesized sweeper HP83651A, and a test set HP8517B were used as measuring devices. These devices and a cylindrical cavity resonator (inner diameter ⁇ 42 mm, height 30 mm) were set up. The resonance frequency, 3 dB bandwidth, transmitted power ratio, etc. were measured at a frequency of 25 GHz with and without inserting the test piece into the resonator. Then, by analytically calculating these measurement results with software, the dielectric properties such as dielectric constant (Dk) and dielectric loss tangent (Df) were obtained.
  • the measurement mode was TE 011 mode.
  • Mold shrinkage rate For each example and comparative example, the molding shrinkage (after ASM) was measured after molding (ASM: as Mold) for the obtained resin composition, and after the molding, main curing was performed to form a dielectric substrate.
  • the molding shrinkage rate (after PMC) was evaluated under heating conditions (PMC: Post Mold Cure) assuming the production of .
  • a test piece prepared using a low-pressure transfer molding machine ("KTS-15" manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. Mold shrinkage (after ASM) was obtained according to K6911. Furthermore, the obtained test piece was heat-treated at 175° C. for 4 hours, and the molding shrinkage (after PMC) was measured according to JIS K 6911.
  • KTS-15 low-pressure transfer molding machine
  • the glass transition temperature (Tg) and linear expansion coefficients (CTE1, CTE2) of the cured resin composition obtained were measured as follows. First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), the encapsulating resin composition was injection molded at a mold temperature of 175° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. A test piece of 10 mm x 4 mm x 4 mm was obtained. Then, after post-curing the obtained test piece at 175 ° C.
  • KTS-15 low-pressure transfer molding machine
  • thermomechanical analyzer manufactured by Seiko Electronics Industries Co., Ltd., TMA100
  • the measurement temperature range is 0 ° C. to 320 ° C.
  • the heating rate is Measurement was performed under the condition of 5°C/min. From these measurement results, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) were calculated.
  • the bending strength (N/mm 2 ) and bending elastic modulus (N/mm 2 ) of the test piece at room temperature (25° C.) or 260° C. were measured according to JIS K 6911 at a head speed of 5 mm/min. .
  • the rectangular pressure of the resin compositions of Examples and Comparative Examples was measured as follows. First, using a low-pressure transfer molding machine (manufactured by NEC Corporation, 40t manual press), a rectangular mold having a width of 13 mm, a thickness of 1 mm, and a length of 175 mm was molded under conditions of a mold temperature of 175°C and an injection rate of 177 mm 3 /sec. A resin composition was injected into the shaped channel. At this time, a pressure sensor embedded at a position 25 mm from the upstream end of the flow channel was used to measure the change in pressure over time, and the minimum pressure (MPa) during the flow of the resin composition was measured, which was defined as the rectangular pressure. Rectangular pressure is a parameter of melt viscosity, and a smaller numerical value indicates a lower melt viscosity.
  • thermosetting resin composition of the present invention a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent, in other words, a dielectric substrate excellent in balance of these properties can be obtained. became clear.
  • microstrip antenna 12 dielectric substrate 14 radiation conductor plate 16 ground conductor plate 20, 20' microstrip antenna 22 dielectric substrate 24 high dielectric substrate 26 spacer a void

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