KR20230160869A - Thermosetting resin compositions, high frequency devices, dielectric substrates, and microstrip antennas - Google Patents

Abstract

The thermosetting resin composition of the present invention is a thermosetting resin composition containing a thermosetting resin, a high dielectric constant filler having a relative dielectric constant of 10 or more at 25°C and 25GHz, and an active ester compound, and the bending elastic modulus at 25°C is FM ₂₅ . And, when the bending elastic modulus at 260°C is FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ are configured to satisfy _{0.005≤FM260} / _FM25≤0.1 . In addition, the thermosetting resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) a high dielectric constant filler, and the epoxy resin (A) is a biphenyl aralkyl type epoxy resin and/or bi. It contains a phenyl type epoxy resin (excluding biphenyl aralkyl type epoxy resin), the hardener (B) contains an active ester type hardener and a phenol type hardener, and the high dielectric constant filler (C) includes calcium titanate and titanium. Barium acid, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium zirconate titanate, lead zirconate titanate, niobic acid. It contains at least one type selected from barium magnesiumate and calcium zirconate, and contains a high dielectric constant filler (C) in an amount of 30% by mass or more in 100% by mass of the thermosetting resin composition.

Description

Thermosetting resin compositions, high frequency devices, dielectric substrates, and microstrip antennas

The present invention relates to thermosetting resin compositions, high-frequency devices, dielectric substrates, and microstrip antennas.

Recently, wireless communication has become faster, and there is a demand for higher performance and smaller size for the communication devices used. In addition, recently, the capacity of wireless communication has rapidly increased, and accordingly, the frequency of use of transmission signals has been rapidly expanded and increased to higher frequencies. Therefore, the frequency band used by communication devices cannot be accommodated only by the microwave band that has been used conventionally, and is expanding to the millimeter wave band. Against this background, there is a strong demand for improved performance for antennas mounted on communication devices.

Communication devices can be further miniaturized if the dielectric constant of the antenna material (dielectric substrate) built inside the communication device is increased. Additionally, as the dielectric tangent of the dielectric substrate decreases, loss becomes low, which is advantageous for increasing frequency. Therefore, if a dielectric substrate with a high dielectric constant and a small dielectric tangent can be used, it is possible to achieve higher frequencies, further shorten circuits, and miniaturize communication devices.

Patent Document 1 discloses an antenna having a dielectric substrate that is a composite material containing a fluororesin and glass cloth, and a circuit board that is a laminate of an antenna whose two-dimensional roughness Ra of the surface in contact with the fluororesin is less than 0.2 μm. This document describes the dielectric constant and dielectric tangent of a circuit board measured at 1 GHz.

Patent Document 2 discloses a resin composition containing a siloxane-modified polyamideimide resin, a high dielectric constant filler, and an epoxy resin, and the relative dielectric constant of the cured product at 25°C and 1 MHz is 15 or more. In the examples of this document, an example of using barium titanate as this high dielectric constant filler is described.

Patent Document 3 discloses a resin composition containing an epoxy resin, dielectric powder, a nonionic surfactant, and an active ester-based curing agent. The document states that this resin composition can be used as a high-dielectric constant insulating material for electronic components used in the high-frequency region or as a high-k dielectric constant insulating material for a fingerprint sensor. In the examples of this document, an example of using barium titanate as this dielectric powder is described.

Patent Document 4 includes an epoxy resin, a curing agent, and an inorganic filler containing calcium titanate particles and strontium titanate particles in a predetermined amount, and the inorganic filler is selected from the group consisting of silica particles and alumina particles. A resin composition for molding, which further contains at least one type and is used for encapsulating electronic components in high-frequency devices, is disclosed.

Patent Document 1: Japanese Patent Publication No. 2018-41998 Patent Document 2: Japanese Patent Publication No. 2004-315653 Patent Document 3: Japanese Patent Publication No. 2020-105523 Patent Document 4: Japanese Patent Publication No. 6870778

However, in the prior art described in Patent Documents 1 to 4, there was room for improvement in the following points.

In the composite material described in Patent Document 1, it was found that there was room for improvement in terms of high dielectric constant and low dielectric tangent in a higher frequency band, and durability under heat. This is the first task.

In addition, the dielectric substrates described in Patent Documents 1 to 4 have problems with high dielectric constant and low dielectric tangent, and these problems are particularly significant in the high frequency band. This is the second task.

The present inventors have found that the first problem can be solved by controlling the bending modulus ratio at 260°C to 25°C to an appropriate range after using a high dielectric constant filler and an active ester compound together in a thermosetting resin composition. He figured it out and completed the first invention.

That is, the first invention can be shown below.

According to the first invention,

Thermosetting resin,

A high dielectric constant filler with a relative dielectric constant of 10 or more at 25°C and 25GHz,

A thermosetting resin composition comprising an active ester compound,

When the bending elastic modulus at 25°C, measured according to the following procedure, is FM ₂₅ and the bending elastic modulus at 260°C is FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ are 0.005 ≤ FM ₂₆₀ /FM ₂₅ ≤ satisfying 0.1,

A thermosetting resin composition is provided.

(sequence)

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 to obtain a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm.

The obtained molded article was post-cured at 175°C for 4 hours, and a test piece was produced.

The bending elastic modulus (N/mm ² ) of the test piece at room temperature (25°C) or 260°C is measured based on JIS K 6911.

Additionally, according to the first invention,

A high-frequency device comprising a cured product of the thermosetting resin composition is provided.

Additionally, the present inventors found that the second problem could be solved by combining specific components, and completed the second invention.

That is, the second invention can be shown below.

According to the second invention,

(A) epoxy resin,

(B) a curing agent,

(C) A thermosetting resin composition comprising a high dielectric constant filler,

The epoxy resin (A) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin (excluding the biphenyl aralkyl type epoxy resin),

The curing agent (B) includes an active ester-based curing agent and a phenol-based curing agent,

The high dielectric constant filler (C) is calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, and titanate. It contains at least one kind selected from calcium zirconate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate, and 30% by mass of a high dielectric constant filler (C) in 100% by mass of the thermosetting resin composition. A thermosetting resin composition containing the above amount can be provided.

According to the second invention,

A dielectric substrate formed by curing the thermosetting resin composition is provided.

According to the first or second invention,

The dielectric substrate,

a radiation conductor plate provided on one side of the dielectric substrate;

A microstrip antenna is provided, including a conductor plate provided on the other side of the dielectric substrate.

According to the first or second invention,

a dielectric substrate,

a radiation conductor plate provided on one side of the dielectric substrate;

a conductive plate provided on the other side of the dielectric substrate;

A microstrip antenna comprising a high dielectric material disposed opposite to the radiation conductor plate,

A microstrip antenna is provided in which the high dielectric constant is constituted by the dielectric substrate.

According to the first invention, it is possible to provide a thermosetting resin composition capable of forming a member with high dielectric constant, low dielectric tangent, and excellent thermal durability, and a high-frequency device using the same.

In addition, according to the second invention, a dielectric substrate excellent in high dielectric constant and low dielectric tangent is obtained, a thermosetting resin composition excellent in moldability, a dielectric substrate made of the resin composition, and a microstrip antenna comprising the dielectric substrate. can be provided. In other words, the thermosetting resin composition of the second invention can provide a dielectric substrate with an excellent balance of high dielectric constant and low dielectric tangent.

1 is a top perspective view showing the microstrip antenna of this embodiment.
Fig. 2 is a cross-sectional view showing another aspect of the microstrip antenna of this embodiment.

Hereinafter, the first invention (claims 1 to 13, 22 to 24 at the time of application) will be described with reference to the drawings based on the first embodiment, and the second invention (claims 14 to 21, 22 to 24 at the time of application) will be described. Based on 2 embodiments, description will be made with reference to the drawings.

In addition, in all drawings, like components are given the same reference numerals and descriptions are omitted as appropriate. Also, for example, “1 to 10” represents “1 or more” to “10 or less” unless otherwise specified.

[First invention]

An outline of the thermosetting resin composition of the first embodiment will be described.

The thermosetting resin composition of the present embodiment includes a thermosetting resin, a high dielectric constant filler having a relative dielectric constant of 10 or more at 25°C and 25 GHz, and an active ester compound, and the bending at 25°C is measured according to the following procedure. When the elastic modulus is FM ₂₅ and the bending elastic modulus at 260°C is FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ are configured to satisfy _{0.005≤FM260} / _FM25≤0.1 .

The lower limit of FM ₂₆₀ /FM ₂₅ is 0.005 or more, preferably 0.006 or more, more preferably 0.007 or more, and even more preferably 0.008 or more. As a result, in a member (cured product of a thermosetting resin composition) having a good high dielectric constant and a good low dielectric tangent, durability under heat can be improved.

On the other hand, the upper limit of FM ₂₆₀ /FM ₂₅ may be, for example, 0.1 or less, preferably 0.05 or less, more preferably 0.03 or less, and further preferably 0.02 or less. Thereby, it is possible to achieve balance in the physical properties of the cured product of the thermosetting resin composition.

Currently, the temperature of the operating environment tends to gradually increase due to design circumstances such as higher frequencies, higher output of power semiconductors, and lower profile of devices. In order to respond to such higher temperatures in the operating environment, the inventor studied the thermal properties of the cured product of the thermosetting resin composition.

According to the present inventor's knowledge, the above-mentioned index FM ₂₆₀ / FM ₂₅ can stably evaluate the difficulty of deformation of a cured product of a thermosetting resin composition before and after heat treatment. And, by setting the indicator FM ₂₆₀ /FM ₂₅ to the above lower limit or more, thermal deterioration of the cured product due to heating can be suppressed, and it has been found that the heat durability of a member formed using the cured product can be improved. .

In addition, in the above-mentioned member, it can be expected that the decline in dielectric properties due to thermal deterioration is suppressed.

In this embodiment, for example, by appropriately selecting the type and mixing amount of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, etc., FM ₂₆₀ /FM ₂₅ above, FS ₂₆₀ /FS ₂₅ below, and glass transition It is possible to control the temperature and coefficient of linear expansion. Among these, for example, the use of calcium titanate as a high dielectric constant filler, the content of the high dielectric constant filler, the further use of alumina as an inorganic filler, and the biphenyl type epoxy resin and/or biphenylene skeleton as the thermosetting resin. Combination use of a phenol aralkyl type epoxy resin and an active ester compound containing a dicyclopentadiene type diphenol structure as an active ester compound, and a biphenyl aralkyl type resin and/or a phenol containing a biphenylene skeleton as a phenolic curing agent. Aralkyl type resins and the like can be cited as elements for bringing the above FM ₂₆₀ /FM ₂₅ , the below FS ₂₆₀ /FS ₂₅ , glass transition temperature, and linear expansion coefficient into the desired numerical ranges.

In addition, the thermosetting resin composition has a bending strength at 25°C of FS ₂₅ , measured at a head speed of 5 mm/min in accordance with JIS K 6911 according to the above procedure, and a bending strength at 260°C of FS. When set to ₂₆₀ , FS ₂₅ and FS ₂₆₀ may be configured to satisfy 0.025 ≤ FS ₂₆₀ /FS ₂₅ ≤ 0.2.

The lower limit of FS ₂₆₀ /FS ₂₅ is 0.025 or more, preferably 0.028 or more, more preferably 0.030 or more, and even more preferably 0.032 or more. Thereby, in a member (cured product of a thermosetting resin composition) with good high dielectric constant and good low dielectric tangent, it is possible to have good thermal toughness.

On the other hand, the upper limit of FS ₂₆₀ /FS ₂₅ may be, for example, 0.2 or less, preferably 0.1 or less, more preferably 0.07 or less, and further preferably 0.05 or less. Thereby, it is possible to achieve balance in the physical properties of the cured product of the thermosetting resin composition.

(Measurement procedures for bending elastic modulus and bending strength)

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 to obtain a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm.

The obtained molded article was post-cured at 175°C for 4 hours, and a test piece was produced.

In accordance with JIS K 6911, the bending elastic modulus (N/mm ² ) and bending strength (N/mm ² ) of the test piece are measured at room temperature (25°C) and 260°C at a head speed of 5 mm/min. .

The lower limit of the glass transition temperature of the cured product of the thermosetting resin composition is, for example, 100°C or higher, preferably 103°C or higher, and more preferably 105°C or higher.

The upper limit of the glass transition temperature in the cured product is not particularly limited, but may be, for example, 250°C or lower.

In the cured product of the thermosetting resin composition, the linear expansion coefficient in the range below the glass transition temperature is set to CTE1, and the linear expansion coefficient in the range above the glass transition temperature up to 320°C is set to CTE2.

CTE1 is, for example, 5 ppm/°C or more and 25 ppm/°C or less, preferably 5 ppm/°C or more and 23 ppm/°C or less.

CTE2 is, for example, 30 ppm/°C or more and 100 ppm/°C or less, preferably 30 ppm/°C or more and 90 ppm/°C or less.

Hereinafter, each component of the thermosetting resin composition of the present embodiment will be described in detail.

[Thermosetting resin]

The thermosetting resin composition of this embodiment contains a thermosetting resin.

As the thermosetting resin, one or two or more types selected from epoxy resin, cyanate resin, and maleimide resin can be used. Among these, epoxy resin may be used.

As an epoxy resin, all monomers, oligomers, and polymers having two or more epoxy groups in one molecule can be used, and their molecular weight or molecular structure are not limited.

Epoxy resins include, for example, biphenyl type epoxy resins; Bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and tetramethylbisphenol F-type epoxy resin; Stilbene type epoxy resin; Novolak-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins; Polyfunctional epoxy resins such as triphenol methane type epoxy resin, exemplified by triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, etc.; Phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene skeleton, naphthol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having a biphenylene skeleton, and naphthol aralkyl type epoxy resins having a biphenylene skeleton. epoxy resin; Epoxy resin containing a biphenylene skeleton; Naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl ethering a dimer of dihydroxynaphthalene; Triazine core-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and cyclic hydrocarbon compound-modified phenol-type epoxy resins such as dicyclopentadiene-modified phenol-type epoxy resins. These may be used individually or two or more types may be used in combination.

Among these, epoxy resins containing a biphenylene skeleton are preferred, and include at least one selected from the group consisting of biphenyl aralkyl type epoxy resins and biphenyl type epoxy resins (excluding biphenyl aralkyl type epoxy resins). It is more desirable to do so.

The content of the thermosetting resin is, for example, 2% by mass or more, preferably 5% by mass or more, and more preferably 7% by mass or more, based on 100% by mass of the thermosetting resin composition.

Additionally, the content of the epoxy resin may be, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, based on 100% by mass of the thermosetting resin composition.

[High dielectric constant filler]

The thermosetting resin composition of this embodiment contains a high dielectric constant filler (high dielectric constant filler).

High dielectric constant fillers include calcium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium zirconate titanate, and zircon titanate. Examples include lead acid, barium magnesium niobate, and calcium zirconate, and one or two or more types selected from these can be used.

Among the above examples, the high dielectric constant filler may contain at least one of calcium titanate and strontium titanate, and preferably contains calcium titanate. As a result, the dielectric tangent in the high frequency band can be further reduced.

The average particle diameter of the high dielectric constant filler is, for example, preferably 0.1 μm or more and 50 μm or less, more preferably 0.3 μm or more and 20 μm or less, and still more preferably 0.5 μm or more and 10 μm or less.

The shape of the high dielectric constant filler is granular, irregular, flake, etc., and the high dielectric constant filler of these shapes can be used in an arbitrary ratio.

The content of the high dielectric constant filler is preferably 30% by mass to 90% by mass, more preferably 35% by mass to 80% by mass, and still more preferably 40% by mass to 70% by mass, based on 100% by mass of the thermosetting resin composition. It is a range. If the addition amount of the high dielectric constant filler is within the above range, the dielectric constant of the obtained cured product becomes lower and the manufacture of molded articles is also excellent.

[Active ester compound]

The thermosetting resin composition of this embodiment contains an active ester compound (active ester curing agent).

The active ester compound functions as a curing agent for thermosetting resins such as epoxy resins.

As the active ester compound, a compound having one or more active ester groups in one molecule can be used. Among them, active ester compounds include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. This is desirable.

Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolak, and an active ester compound containing a phenol novolac. and active ester compounds containing benzoylides. The active ester compound may include at least one selected from these.

Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. “Dicyclopentadiene-type diphenol structure” refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

In this embodiment, the active ester compound can be, for example, a resin having a structure represented by the following general formula (1).

In formula (1), “B” is the structure represented by formula (B).

In formula (B), Ar is a substituted or unsubstituted arylene group. Substituents of the substituted arylene group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group.

Y is a single bond, a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, or a substituted or unsubstituted divalent aromatic hydrocarbon group, It is an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group. Examples of the substituent for the above group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group.

Preferred examples of Y include a single bond, methylene group, -CH(CH ₃ ) ₂ -, ether bond, optionally substituted cycloalkylene group, optionally substituted 9,9-fluorenylene group, etc.

n is an integer from 0 to 4, and is preferably 0 or 1.

B is, specifically, a structure represented by the following general formula (B1) or the following general formula (B2).

In the general formula (B1) and (B2), Ar and Y have the same meaning as in general formula (B).

A is a substituted or unsubstituted arylene group connected through an aliphatic cyclic hydrocarbon group,

Ar' is a substituted or unsubstituted aryl group,

k is the average value of the repeating unit and ranges from 0.25 to 3.5.

The thermosetting resin composition of the present embodiment contains a specific active ester compound, so that the obtained cured product can have excellent dielectric properties and has an excellent low dielectric tangent.

The active ester compound used in the thermosetting resin composition of this embodiment has an active ester group represented by formula (B). In the curing reaction between an epoxy resin and an active ester compound, the active ester group of the active ester compound reacts with the epoxy group of the epoxy resin to generate secondary hydroxyl groups. This secondary hydroxyl group is blocked by the ester residue of the active ester compound. Therefore, the dielectric tangent of the cured product is reduced.

In one embodiment, the structure represented by the formula (B) is preferably at least one selected from the following formulas (B-1) to (B-6).

In formulas (B-1) to (B-6),

R ¹ is 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,

R ² is each independently any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and , a carbonyloxy group, a sulfide group, or a sulfone group,

n is an integer from 0 to 4, and p is an integer from 1 to 4.

Since the structures represented by the above formulas (B-1) to (B-6) are all structures with high orientation, when an active ester compound containing this is used, the cured product of the resulting thermosetting resin composition has a high orientation in the high frequency range. It can have a low dielectric tangent of .

Among them, from the viewpoint of low dielectric tangent, active ester compounds having a structure represented by formula (B-2), formula (B-3) or formula (B-5) are preferable, and n in formula (B-2) An active ester compound having a structure in which X is 0, a structure in which desirable. Moreover, it is preferable that all R ¹ in each formula are hydrogen atoms.

"Ar'" in formula (1) is an aryl group, for example, 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-(α-cumyl)phenyl group, 1-naphthyl group, 2-naphthyl group, etc. Among them, a 1-naphthyl group or a 2-naphthyl group is preferable because a cured product with a particularly low dielectric tangent can be obtained.

In the present embodiment, [A] in the active ester compound represented by formula (1) is a substituted or unsubstituted arylene group linked through an aliphatic cyclic hydrocarbon group, and such an arylene group includes, for example, one molecule A structure obtained by polyaddition reaction of an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds and a phenolic compound is included.

The unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule is, for example, dicyclopentadiene, cyclopentadiene multimer, tetrahydroindene, 4-vinylcyclohexene, 5- Examples include vinyl-2-norbornene and limonene, and these may be used individually or in combination of two or more types. Among these, dicyclopentadiene is preferable because a cured product excellent in heat resistance is obtained. In addition, since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain cyclopentadiene multimers and other aliphatic or aromatic diene compounds as impurities, but the heat resistance is low. Considering performance such as curability and moldability, it is preferable to use a product with a purity of 90% by mass or more of dicyclopentadiene.

Meanwhile, the phenolic compounds include, for example, phenol, cresol, xylenol, ethyl phenol, isopropyl phenol, butyl phenol, octyl phenol, nonyl phenol, vinyl phenol, isopropenyl phenol, allyl phenol, phenyl phenol, Benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene Hydroxynaphthalene etc. are mentioned, and each may be used individually, or two or more types may be used together. Among these, phenol is preferable because it provides an active ester compound with high curability and excellent dielectric properties in the cured product.

In a preferred embodiment, [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 realize a low dielectric tangent in the high frequency band.

In equation (A),

R ³ is 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,

l is 0 or 1, and m is an integer of 1 or more.

Among the active ester compounds represented by the formula (1), resins represented by the following formulas (1-1), (1-2) and (1-3) can be cited as more preferable ones, and particularly preferable ones include the following formulas: Resins represented by (1-3) can be mentioned.

In formula (1-1), R ¹ and R ³ are each independently any one of a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group, and an aralkyl group, and Z is It is a phenyl group or naphthyl group having 1 to 3 alkyl groups of 1 to 4 carbon atoms on the phenyl group, naphthyl group, or aromatic nucleus, l is 0 or 1, k is the average of the repeating unit, and is 0.25 to 3.5.

In formula (1-2), R ¹ and R ³ are each independently any one of a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group, and an aralkyl group, and Z is It is a phenyl group or naphthyl group having 1 to 3 alkyl groups of 1 to 4 carbon atoms on the phenyl group, naphthyl group, or aromatic nucleus, l is 0 or 1, k is the average of the repeating unit, and is 0.25 to 3.5.

In formula (1-3), R ¹ and R ³ are each independently any one of a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group, and an aralkyl group, and Z is It is a phenyl group or naphthyl group having 1 to 3 alkyl groups of 1 to 4 carbon atoms on the phenyl group, naphthyl group, or aromatic nucleus, l is 0 or 1, k is the average of the repeating unit, and is 0.25 to 3.5.

The active ester compound represented by the general formula (A) includes a phenolic compound (a) having a structure in which an aryl group having a phenolic hydroxyl group is multiple knotted through an aliphatic cyclic hydrocarbon group, and an aromatic nucleus-containing dicarboxylic acid or halide thereof (b) ) and an aromatic monohydroxy compound (c) can be produced by a known method.

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 adjusted appropriately according to the desired molecular design, but among them, more curable properties are preferred. In order to obtain a highly active ester compound, the phenolic hydroxyl group of the phenolic compound (a) is 0.25 to 1 mole in total of the carboxyl group or acid halide group of the aromatic nucleus-containing dicarboxylic acid or its halide (b). It is preferable to use each raw material in a ratio that is in the range of 0.90 mol, and the hydroxyl group of the aromatic monohydroxy compound (c) is in the range of 0.10 to 0.75 mol, and the phenolic compound (a) It is more preferable to use each raw material in a ratio such that the phenolic hydroxyl group of the aromatic monohydroxy compound (c) is in the range of 0.50 to 0.75 mol, and the hydroxyl group of the aromatic monohydroxy compound (c) is in the range of 0.25 to 0.50 mol. do.

In addition, the equivalent weight of the functional group of the active ester compound is 200 g/g, because when the total of the arylcarbonyloxy group and phenolic hydroxyl group in the resin structure is taken as the number of functional groups in the resin, a cured product with excellent curability and low dielectric tangent is obtained. It is preferable that it is in the range of 230 g/eq or less, and more preferably 210 g/eq or more and 220 g/eq or less.

In the thermosetting resin composition of the present embodiment, the content of the active ester compound and the epoxy resin is set to 1 equivalent of the total of active groups in the active ester compound, since a cured product with excellent curability and low dielectric tangent is obtained. It is preferable that the epoxy group in the ratio is 0.8 to 1.2 equivalents. Here, the active group in the active ester compound refers to the arylcarbonyloxy group and phenolic hydroxyl group contained in the resin structure.

The active ester compound 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, and still more preferably 2% by mass or more and 9% by mass or less, in 100% by mass of the thermosetting resin composition. It is used in the amount of

By including a specific active ester compound in the above range, the resulting cured product can have better dielectric properties and a better low dielectric tangent.

The thermosetting resin composition of the present embodiment has superior high dielectric constant and low dielectric tangent by using the active ester compound and the above-mentioned high dielectric constant filler in combination, and these effects are excellent even in the high frequency band.

From the viewpoint of the above effect, the active ester compound is preferably contained in an amount of 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 or less, more preferably, with respect to 100 parts by mass of the high dielectric constant filler described above. may be included in an amount of 3 parts by mass or more and 15 parts by mass or less.

[Hardener]

The thermosetting resin composition of this embodiment may contain a curing agent other than the active ester compound.

As other curing agents, phenol-based curing agents, amine compound-based curing agents, amide compound-based curing agents, acid anhydride-based curing agents, etc. are used. These may be used individually or two or more types may be used in combination. Among them, a phenol-based curing agent may be used.

Phenol-based curing agents include, for example, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol addition type resin, phenol resin containing a biphenylene skeleton, and phenol aralkyl. Resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol coaxial novolak resin, naphthol-cresol coaxial novolak resin, biphenyl modified phenolic resin (with bismethylene group) polyhydric phenol compounds with phenol nuclei linked), biphenyl-modified naphthol resins (polyhydric naphthol compounds with phenol nuclei linked with bismethylene groups), aminotriazine-modified phenol resins (polyhydric phenol compounds with phenol nuclei linked with melamine, benzoguanamine, etc.), etc. polyhydric phenol compounds.

Among these, biphenyl aralkyl type phenol resin can be used.

Amine compound-based curing agents include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, guanidine derivatives, etc. Amine compounds can be mentioned.

Examples of the amide compound-based curing agent include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid, and ethylenediamine.

Acid anhydride-based curing agents include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl. Hexahydrophthalic anhydride may be mentioned.

When using a curing agent, the compounding amount is preferably 0.5 mass% or more and 15 mass% or less, more preferably 1 mass% or more and 10 mass% or less, based on 100 mass% of the thermosetting resin. By using the curing agent in an amount within the above range, a thermosetting resin composition having excellent curing properties is obtained.

[Curing catalyst]

The thermosetting resin composition may contain a curing catalyst.

The curing catalyst is sometimes 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 a known curing catalyst can be used.

Specifically, phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; Imidazoles such as 2-methylimidazole and 2-phenylimidazole (imidazole-based curing accelerator); Nitrogen atom-containing compounds such as amidines and tertiary amines, such as 1,8-diazabicyclo[5.4.0]undecene-7 and benzyldimethylamine, and quaternary salts of amidines and amines, are included. Yes, only one type may be used, or two or more types may be used.

Among these, from the viewpoint of improving hardenability and obtaining a magnetic material with excellent mechanical strength such as bending strength, it is preferable to include a phosphorus atom-containing compound, and include tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphine compounds and quinone compounds. It is more preferable to include those having latent properties, such as adducts of phosphonium compounds and silane compounds, tetra-substituted phosphonium compounds, adducts of phosphine compounds and quinone compounds, and phosphonium compounds and silane compounds. Adducts of compounds are particularly preferred.

By using the compound (C) represented by the general formula (1) in combination with a latent curing catalyst, a magnetic material with superior moldability and mechanical strength such as bending strength can be obtained.

Examples of organic phosphines include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; Tertiary phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine can be mentioned.

When using a curing catalyst, 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 this numerical range, a sufficient curing acceleration effect can be obtained without excessively deteriorating other performances.

[Inorganic filler]

The thermosetting resin composition of the present embodiment may further include an inorganic filler in addition to a high dielectric constant filler in order to reduce hygroscopicity, reduce linear expansion coefficient, improve thermal conductivity, and improve strength.

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, forsterite, steatite, spinel, Examples include powders such as mullite and titania, beads obtained by sphericalizing them, and glass fibers. These inorganic fillers may be used individually or in combination of two or more types. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, alumina is preferable from the viewpoint of high thermal conductivity, and the shape of the filler is preferably spherical from the viewpoint of fluidity during molding and mold wear resistance.

The content of inorganic fillers other than the high dielectric constant filler is preferably 3% by mass or more and 60% by mass or less, more preferably 5% by mass, based on 100% by mass of the thermosetting resin composition, from the viewpoint of reducing moldability, thermal expansion, and improving strength. It can be in the range of 50% by mass or more and 50% by mass or less. Within the above range, thermal expansion is reduced and moldability is excellent.

[Other ingredients]

In addition to the above components, the thermosetting resin composition of the present embodiment may, if necessary, contain various components such as a silane coupling agent, a mold release agent, a colorant, a dispersant, and a stress reducing agent.

In particular, silane coupling agents include amino group-containing silane coupling agents and mercapto group-containing silane coupling agents. Moreover, from the viewpoint of homogeneous mixing of the high dielectric constant filler and the inorganic filler, the mixing properties of the high dielectric constant filler and organic components such as epoxy resin, and the viewpoint of bending strength and bending elastic modulus, it is preferable to use two or more of them.

[Thermosetting resin composition]

The thermosetting resin composition of this embodiment can be manufactured by uniformly mixing each of the components described above. The manufacturing method includes sufficiently mixing raw materials with a predetermined content using a mixer or the like, melting and kneading them using a mixing roll, kneader, or extruder, followed by cooling and pulverizing. If necessary, the obtained thermosetting resin composition may be tableted with a size and mass suitable for molding conditions.

The cured product obtained from the thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric tangent in the high frequency band, and thus can achieve high frequency, shortening of circuits, and miniaturization of high frequency devices such as communication equipment. there is.

Such a 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.

Below, an example of a high-frequency device will be described.

<Microstrip antenna>

As shown in FIG. 1, the microstrip antenna 10 includes a dielectric substrate 12 formed by curing the thermosetting resin composition described above, and a radiating conductor plate (radiating element) provided on one side of the dielectric substrate 12 ( 14) and a conductor plate 16 provided on the other side of the dielectric substrate 12.

The shape of the radiation conductor plate may be rectangular or circular. The present embodiment will be explained by an example using a rectangular radiation conductor plate 14.

The radiation conductor plate 14 contains any one of a metal material, an alloy of a metal material, a cured product of a metal paste, and a conductive polymer. Metal materials include copper, silver, palladium, gold, platinum, aluminum, chromium, nickel, cadmium, lead, selenium, manganese, tin, vanadium, lithium, cobalt, and titanium. An alloy contains multiple metal materials. A metal paste agent contains a powder of a metal material mixed with an organic solvent and a binder. The binder includes epoxy resin, polyester resin, polyimide resin, polyamideimide resin, and polyetherimide resin. Conductive polymers include polythiophene-based polymers, polyacetylene-based polymers, polyaniline-based polymers, and polypyrrole-based polymers.

As shown in FIG. 1, the microstrip antenna 10 of the present embodiment has a radiation conductor plate 14 of length L and width W, and L resonates at a frequency equal to an integer multiple of 1/2 wavelength. do. When using the dielectric substrate 12 having a high dielectric constant as in this embodiment, 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 conductive plate 16 is a thin plate made of a highly conductive metal such as copper, silver, or gold. The thickness is sufficiently thin relative to the central operating frequency of the antenna device, and may be about 1/50th to 1/1000th of the wavelength of the central operating frequency.

Feeding methods for microstrip antennas include direct feeding methods such as back-coaxial feeding and co-planar feeding, and electromagnetic-coupled feeding methods such as slot-coupled feeding and proximity-coupled feeding.

Back coaxial power can be fed from the back of the antenna to the radiation conductor plate 14 using a coaxial line or connector that passes through the conductor plate 16 and the dielectric substrate 12.

Coplanar power supply can feed power to the radiation conductor plate 14 through a microstrip line (not shown) disposed on the same plane as the radiation conductor plate 14.

In slot-coupled power feeding, another dielectric substrate (not shown) is prepared with the conductor plate 16 sandwiched between them, and the radiation conductor plate 14 and the microstrip line are formed on a separate dielectric substrate. The radiation conductor plate 14 is excited by electromagnetic coupling between the radiation conductor plate 14 and the microstrip line through the slot formed in the conductor plate 16.

In close-coupled power supply, the dielectric substrate 12 has a laminated structure, and the dielectric substrate on which the radiating conductor plate 14 is formed and the dielectric substrate on which the strip conductors of the microstrip line and the conductor plate 16 are arranged are laminated. . The radiation conductor plate 14 is excited by extending the strip conductor of the microstrip line to the lower part of the radiation conductor plate 14 and electronically coupling the radiation conductor plate 14 and the microstrip line.

Figures 2 (a) and (b) show other aspects of a microstrip antenna. In addition, the same components as those in FIG. 1 are assigned the same numbers and descriptions are omitted as appropriate.

As shown in Figure 2 (a), the microstrip antenna 20 includes a dielectric substrate 22, a radiation conductor plate 14 provided on one side of the dielectric substrate 22, and the dielectric substrate 22. It is provided with a conductor plate 16 provided on the other side of and a high dielectric substrate (high dielectric material) 24 disposed opposite to the radiation conductor plate 14. The dielectric substrate 22, the radiation conductor plate 14, and the high dielectric substrate 24 can be configured to be spaced apart by a predetermined distance through a spacer 26.

The dielectric substrate 22 is made of a low dielectric constant substrate such as a Teflon substrate.

The high-dielectric substrate 24 is comprised of a dielectric substrate formed by curing the above-described resin composition.

The gap between the dielectric substrate 22 and the high dielectric substrate 24 may be empty or may be filled with a dielectric material.

Additionally, as shown in the microstrip antenna 20' in FIG. 2(b), a structure may be used in which a high dielectric substrate 24 is brought into contact with the upper surface of the radiation conductor plate 14.

<Dielectric waveguide>

In this embodiment, the dielectric waveguide includes a dielectric formed 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) and transmits them.

The conductor film can be made of a metal such as copper or an oxide high-temperature superconductor.

<Multilayer antenna>

In this embodiment, the multilayer antenna is provided with a dielectric sheet formed by curing the thermosetting resin composition of this embodiment.

Specifically, a multilayer antenna is a module in which a circuit consisting of a large number of elements such as condensers and inductors is printed and stacked on a dielectric sheet.

[Second invention]

The thermosetting resin composition of the second embodiment includes an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C), and the high dielectric constant filler (C) is 30% by mass or more out of 100% by mass of the composition. Includes.

[Epoxy Resin (A)]

In this embodiment, the epoxy resin (A) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin (excluding the biphenyl aralkyl type epoxy resin).

The biphenyl aralkyl type epoxy resin of the present embodiment preferably has a structural unit represented by general formula (a) below.

In general formula (a),

R ^a and R ^b , when present in plural, are each independently a monovalent organic group, hydroxyl group, or halogen atom,

r and s are each independently 0 to 4,

* indicates that it is connected to another atomic group.

Specific examples of the monovalent organic groups of R ^a and R ^b include alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, alkoxy group, heterocyclic group, carboxyl group, etc. You can.

Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, and heptyl group. , octyl group, nonyl group, decyl group, etc.

Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group.

Examples of the alkyne group include ethyne group.

Examples of the alkylidene group include methylidene group and ethylidene group.

Examples of the aryl group include tolyl group, xylyl group, phenyl group, naphthyl group, and anthracenyl group.

Examples of aralkyl groups include benzyl group and phenethyl group.

Examples of the alkaryl group include tolyl group and xylyl group.

Examples of cycloalkyl groups include adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, Neopentyloxy group, n-hexyloxy group, etc. can be mentioned.

Examples of heterocyclic groups include epoxy groups and oxetane groups.

The total carbon number of the monovalent organic groups of R ^a and R ^b is, for example, 1 to 30, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6.

r and s are each independently, preferably 0 to 2, more preferably 0 to 1. In one aspect, r and s are both 0.

R ^c , when present in plural, is each independently a monovalent organic group, a hydroxyl group, or a halogen atom,

t is an integer from 0 to 3.

Specific examples of the monovalent organic group of R ^c include the same groups as those given as specific examples of R ^a and R ^b .

t is preferably 0 to 2, and more preferably 0 to 1.

The weight average molecular weight Mw of the biphenyl aralkyl type epoxy resin of this embodiment is preferably 500 or more and 2000 or less, more preferably 600 or more and 1900 or less, and still more preferably 700 or more and 1800 or less.

Moreover, the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the biphenyl aralkyl type epoxy resin is preferably 2.0 or more and 4.0 or less, more preferably 1.8 or more and 3.8 or less, and still more preferably 1.6 or more and 3.6 or less. . By appropriately adjusting the degree of dispersion, the physical properties of the epoxy resin can be made uniform, which is preferable.

For the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn), for example, polystyrene conversion values obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement are used. The measurement conditions for GPC measurement are, for example, as follows.

Tosoh Gel Permeation Chromatography Apparatus HLC-8320GPC

Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation

Detector: RI detector for liquid chromatograms

Measurement temperature: 40℃

Solvent: THF

Sample concentration: 2.0 mg/milliliter

The biphenyl type epoxy resin of this embodiment can be represented by general formula (b) below.

In general formula (b), R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms.

As the biphenyl type epoxy resin, specifically, diglycidyl ether of 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxybi. Diglycidyl ether of phenyl, diglycidyl ether of 3,3',5,5'-tetratert-butyl-4,4'-dihydroxybiphenyl, diglycidyl ether of dimethyldipropylbiphenol Glycidyl ether, diglycidyl ether of dimethyl biphenol, etc. are mentioned.

The epoxy resin (A) may further contain other epoxy resins in addition to the above two types of epoxy resins, to the extent that the effects of the present invention are not impaired.

Other epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol aralkyl-type epoxy resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, and glycidylamine-type epoxy resin. .

In this embodiment, the content of "biphenyl aralkyl type epoxy resin and/or biphenyl type epoxy resin" in the epoxy resin (A) is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass. % or more and 100 mass% or less, more preferably 80 mass% or more and 100 mass% or less, and the epoxy resin (A) may contain only these two types of epoxy resins.

From the viewpoint of the effect of the present invention, the thermosetting resin composition (100% by mass) of the present embodiment preferably contains 2% by mass or more and 30% by mass or less of the epoxy resin (A), more preferably 3% by mass or more and 25% by mass. % or less, more preferably 5 mass% or more and 20 mass% or less.

[Hardener (B)]

In this embodiment, the curing agent (B) includes an active ester-based curing agent and a phenol-based curing agent. By including these curing agents in combination, a dielectric substrate with excellent high dielectric constant and low dielectric tangent can be obtained, and a thermosetting resin composition with excellent moldability can be obtained.

(Activated ester hardener)

As the active ester-based curing agent, the same active ester compound as described in the embodiment of the first invention can be used, and it can be manufactured in the same way.

When the active ester-based curing agent is a resin having a structure represented by the above general formula (1), it is preferable that “B” in the above general formula (1) has a structure represented by the above formulas (B-1) to (B-6). do. Since the structures represented by the above formulas (B-1) to (B-6) are all structures with high orientation, when an active ester-based curing agent containing this is used, the cured product of the thermosetting resin composition obtained has a low dielectric tangent. It has excellent adhesion to metals, and therefore can be suitably used as a semiconductor encapsulation material.

In addition, the functional group equivalent of the active ester-based curing agent is 200 g, because when the sum of the arylcarbonyloxy group and phenolic hydroxyl group in the resin structure is taken as the number of functional groups in the resin, a cured product with excellent curability and low dielectric tangent is obtained. It is preferable that it is in the range of /eq to 230 g/eq, and it is more preferable that it is in the range of 210 g/eq or more and 220 g/eq or less.

In the thermosetting resin composition of the present embodiment, the mixing amount of the activated ester curing agent and the epoxy resin is set to obtain a cured product with excellent curability and a low dielectric tangent, with respect to 1 equivalent of the total of active groups in the active ester curing agent. It is preferable that the ratio of epoxy groups in the epoxy resin is 0.8 to 1.2 equivalents. Here, the active group in the active ester-based curing agent refers to the arylcarbonyloxy group and phenolic hydroxyl group contained in the resin structure.

In the composition of this embodiment, the active ester curing agent is 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, with respect to the entire thermosetting resin composition. It is used in an amount of 1.0 mass% or more and 7 mass% or less.

By including a specific active ester-based curing agent in the above range, the resulting cured product can have better dielectric properties and a better low dielectric tangent.

The resin composition of the present embodiment is superior in high dielectric constant and low dielectric tangent by using a combination of an active ester-based curing agent and a high dielectric constant filler described later, and these effects are excellent even in the high frequency band.

From the viewpoint of the above effect, the active ester-based curing agent 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 or less, with respect to 100 parts by mass of the high dielectric constant filler described later. In other words, it may be included in an amount of 3 parts by mass or more and 15 parts by mass or less.

In addition, as described in Japanese Patent Application Publication No. 2020-90615, the present applicant is developing 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 technology described in the publication in that it contains a high dielectric constant filler. In addition, since it contains a high dielectric constant filler, the effect of the combination of an active ester-based curing agent and an epoxy resin is also different in that it has a high dielectric constant and is excellent in high dielectric constant and low dielectric tangent in the high frequency band.

(Phenol-based hardener)

Examples of the phenolic curing agent include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, Tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol coaxial novolak resin, naphthol-cresol coaxial novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound with a phenol nucleus linked to a bismethylene group), biphenyl-modified naphthol resin Polyhydric phenol compounds such as (polyhydric naphthol compound whose phenol nucleus is connected to a bismethylene group) and aminotriazine-modified phenol resin (polyhydric phenol compound whose phenol nucleus is connected to melamine, benzoguanamine, etc.).

The compounding amount of the phenol-based curing agent is preferably an amount of 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 curing properties is obtained.

The ratio of the content of the phenol-based curing agent b to the active ester-based curing agent a (b (parts by mass)/a (parts by mass)) is preferably 0.5 or more and 8 or less, more preferably 1 or more and 5 or less, further preferably can be 1.5 or more and 3 or less.

By including the active ester-based curing agent and the phenol-based curing agent in the above ratio, the obtained cured product can have better dielectric properties and a better low dielectric tangent.

In the composition of the present embodiment, the curing agent (B) containing an active ester-based curing agent and a phenol-based curing agent is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass, based on the entire thermosetting resin composition. % or more and 10 mass% or less, more preferably 1.0 mass% or more and 7 mass% or less.

By including a specific active ester-based curing agent in the above range, the resulting cured product can have better dielectric properties and a better low dielectric tangent.

[High dielectric constant filler (C)]

In this embodiment, the high dielectric constant filler (C) includes calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, Examples include barium zirconate, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate, and may contain at least one type selected from these. By including these high dielectric constant fillers, a dielectric substrate excellent in high dielectric constant and low dielectric tangent is obtained.

From the viewpoint of the effect of the present invention, the high dielectric constant filler is preferably at least one selected from calcium titanate, strontium titanate, and magnesium titanate, and is further preferably at least one type selected from calcium titanate and magnesium titanate. desirable.

The shape of the high dielectric constant filler is granular, irregular, flake, etc., and the high dielectric constant filler of these shapes can be used in any ratio. The average particle diameter of the high dielectric constant filler is preferably 0.1 μm or more and 50 μm or less, more preferably 0.3 μm or more and 20 μm or less, and still more preferably 0.5 μm or more and 10 μm or less from the viewpoint of the effect of the present invention and fluidity and fillability. am.

The blending amount of the high dielectric constant filler is in the range of 30% by mass or more, preferably 35% by mass or more, more preferably 45% by mass or more, based on 100% by mass of the thermosetting resin composition. The upper limit is about 80% by mass or less.

If the amount of the high dielectric constant filler added is within the above range, the dielectric constant of the obtained cured product becomes lower and the manufacture of molded articles is also excellent.

[Curing Catalyst (D)]

The thermosetting resin composition of this embodiment may further include a curing catalyst (D).

The curing catalyst (D) is sometimes called a curing accelerator or the like. The curing catalyst (D) is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and a known curing catalyst can be used.

As the curing catalyst (D), specifically, phosphorus atoms such as organic phosphine, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Containing compounds; Imidazoles such as 2-methylimidazole and 2-phenylimidazole (imidazole-based curing accelerator); Nitrogen atom-containing compounds such as amidines and tertiary amines, such as 1,8-diazabicyclo[5.4.0]undecene-7 and benzyldimethylamine, and quaternary salts of amidines and amines, are included. Yes, only one type may be used, or two or more types may be used.

Among these, from the viewpoint of improving hardenability and obtaining a magnetic material with excellent mechanical strength such as bending strength, it is preferable to include a phosphorus atom-containing compound, and include tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphine compounds and quinone compounds. It is more preferable to include those having latent properties, such as adducts of phosphonium compounds and silane compounds, tetra-substituted phosphonium compounds, adducts of phosphine compounds and quinone compounds, and phosphonium compounds and silane compounds. Adducts of compounds are particularly preferred.

By using a combination of an epoxy resin (A) containing a naphthol aralkyl type epoxy resin and a latent curing catalyst, a magnetic material with superior moldability and mechanical strength such as bending strength can be obtained.

Examples of organic phosphines include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; Tertiary phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine can be mentioned.

Examples of tetra-substituted phosphonium compounds include compounds represented by the following general formula (6).

In 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 the anion of an aromatic organic acid having at least one functional group selected from hydroxyl group, carboxyl group, and thiol group in the aromatic ring.

AH represents an aromatic organic acid having at least one functional group selected from hydroxyl group, carboxyl group, and thiol group in the aromatic ring.

x, y are 1 to 3, z is 0 to 3, and x=y.

The compound represented by general formula (6) is obtained, for example, as follows.

First, a tetra-substituted phosphonium halide, an aromatic organic acid, and a base are mixed uniformly in an organic solvent, and aromatic organic acid anions are generated within the solution system. If water is then added, the compound represented by general formula (6) can be precipitated. In the compound represented by general formula (6), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in the aromatic ring, that is, a phenol, and A is preferably an anion of the phenol. Examples of the phenols include monocyclic phenols such as phenol, cresol, resocin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, and phenylphenol. and polycyclic phenols such as biphenol.

Examples of the phosphobetaine compound include compounds represented by the following general formula (7).

In 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 to 5, and g is 0 to 3.

The compound represented by general formula (7) is obtained, for example, as follows.

First, it is obtained through a process of bringing a tri-aromatic substituted phosphine, which is the third phosphine, into contact with a diazonium salt, and substituting the diazonium group of the tri-aromatic substituted phosphine and the diazonium salt.

Examples of adducts of a phosphine compound and a quinone compound include compounds represented by the following general formula (8).

In general formula (8),

P represents a phosphorus atom.

R ¹⁰ , R ¹¹ and R ¹² 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 from each other.

R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R ¹⁴ and R ¹⁵ may be combined to form a cyclic structure.

Examples of phosphine compounds used in the adduct of a phosphine compound and a quinone compound include triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trynaphthylphosphine, and tris(benzyl). ) It is preferable that the aromatic ring such as phosphine is unsubstituted or has a substituent such as an alkyl group or alkoxyl group, and substituents such as an alkyl group or alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of ease of availability, triphenylphosphine is preferable.

Moreover, quinone compounds used in the adduct of a phosphine compound and a quinone compound include benzoquinone and anthraquinone, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing both an organic tertiary phosphine and a benzoquinone in a soluble solvent. As a solvent, a ketone such as acetone or methyl ethyl ketone, with low solubility in adducts, is preferred. However, it is not limited to this.

In the compound represented by the general formula (8), R ¹⁰ , R ¹¹ and R ¹² bonded to the phosphorus atom are phenyl groups, and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, that is, 1,4-benzoquine. A compound obtained by adding paddy rice and triphenylphosphine is preferable because it reduces the thermal modulus of elasticity of the cured product of the encapsulating resin composition.

Examples of adducts of a phosphonium compound and a silane compound include compounds represented by the following general formula (9).

In 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 organic group or an aliphatic group having an aromatic ring or a heterocycle, and may be the same or different from each other.

R ²⁰ is an organic group bonded to groups Y ² and Y ³ .

R ²¹ is an organic group bonded to groups Y ⁴ and Y ⁵ .

Y ² and Y ³ represent groups formed by a proton donating group emitting a proton, and groups Y ² and Y ³ in the same molecule combine with a silicon atom to form a chelate structure.

Y ⁴ and Y ⁵ represent groups formed by a proton donating group releasing a proton, and groups Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure.

R ²⁰ and R ²¹ may be the same or different from each other, and Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same as or different from each other.

Z ¹ is an organic group having an aromatic ring or heterocycle, or an aliphatic group.

In general formula (9), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include, 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, and among these, alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, and hydroxynaphthyl group, alkoxy group, and hydroxyl group. An aromatic group having a substituent such as or an unsubstituted aromatic group is more preferable.

In General Formula (9), R ²⁰ is an organic group bonded to Y ² and Y ³ . Likewise, R ²¹ is an organic group bonded to groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by a proton donating group emitting a proton, and groups Y ² and Y ³ in the same molecule combine with a silicon atom to form a chelate structure. Likewise, Y ⁴ and Y ⁵ are groups formed by a proton donating group releasing a proton, and the groups Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. Groups R ²⁰ and R ²¹ may be the same or different from each other, and groups Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same as or different from each other. The groups represented by -Y ² -R ²⁰ -Y ³ - and Y ⁴ -R ²¹ -Y ⁵ - in this general formula (9) are composed of a group formed by the proton donor releasing two protons, and the proton As the donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and furthermore, an aromatic compound having at least two carboxyl groups or hydroxyl groups on adjacent carbons constituting the aromatic ring is preferable, forming the aromatic ring. Aromatic compounds having at least two hydroxyl groups on adjacent carbons are more preferable, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2' -Biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, Examples include 1,2-cyclohexanediol, 1,2-propanediol, and glycerin, but among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene. It is more desirable.

Z ¹ in the general formula (9) represents an organic group or an aliphatic group having an aromatic ring or a heterocycle, and specific examples thereof include aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and octyl group. , aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group, and biphenyl group, glycidyloxy groups such as glycidyloxypropyl group, mercaptopropyl group, and aminopropyl group, mercapto group, alkyl group having amino group, and vinyl group. and reactive substituents such as these, but among these, methyl group, ethyl group, phenyl group, naphthyl group and biphenyl group are more preferable from the viewpoint of thermal stability.

The method for producing an adduct of a phosphonium compound and a silane compound is, for example, as follows.

In a flask filled with methanol, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added and dissolved, and then the sodium methoxide-methanol solution is added dropwise while stirring at room temperature. . Additionally, if a previously prepared solution of a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide dissolved in methanol is added dropwise while stirring at room temperature, crystals are precipitated. When the precipitated crystals are filtered, washed with water, and dried under vacuum, an adduct of a phosphonium compound and a silane compound is obtained.

When using a curing catalyst (D), its content is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass, based on 100% by mass of the thermosetting resin composition. By setting this numerical range, a sufficient curing acceleration effect can be obtained without excessively deteriorating other performances.

[Inorganic filler]

The thermosetting resin composition of the present embodiment may further include an inorganic filler in addition to the high dielectric constant filler (C) in order to reduce hygroscopicity, reduce linear expansion coefficient, improve thermal conductivity, and improve strength.

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, forsterite, steatite, spinel, Examples include powders such as mullite and titania, beads obtained by sphericalizing these particles, and glass fibers. These inorganic fillers may be used individually or in combination of two or more types. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, alumina is preferable from the viewpoint of high thermal conductivity, and the shape of the filler is preferably spherical from the viewpoint of fluidity during molding and mold wear resistance.

The blending amount of the inorganic filler other than the high dielectric constant filler (C) is preferably 10% by mass or more and 50% by mass or less, with respect to 100% by mass of the thermosetting resin composition, from the viewpoint of reducing moldability, thermal expansion, and improving strength. More preferably, it is in the range of 15 mass% or more and 40 mass% or less, and even more preferably 20 mass% or more and 35 mass% or less. Within the above range, thermal expansion is reduced and moldability is excellent.

[Other ingredients]

In addition to the above components, the thermosetting resin composition of the present embodiment may, if necessary, contain various components such as a silane coupling agent, a mold release agent, a colorant, a dispersant, and a stress reducing agent.

The thermosetting resin composition of the present embodiment includes the following epoxy resin (A), the following curing agent (B), and the following high dielectric constant filler (C), and the high dielectric constant filler (C) is added to 100 mass of the composition. It contains more than 30% by mass.

Epoxy resin (A): Contains biphenyl aralkyl type epoxy resin and/or biphenyl type epoxy resin.

Hardener (B): Includes active ester-based hardeners and phenol-based hardeners.

High dielectric constant filler (C): calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, zircon titanate. It contains at least one selected from calcium acid, lead zirconate titanate, barium magnesium niobate, and calcium zirconate.

According to the thermosetting resin composition of the present embodiment formed by combining such components, a dielectric substrate excellent in high dielectric constant and low dielectric tangent can be obtained, and a microstrip antenna including the dielectric substrate can be provided.

The thermosetting resin composition of this embodiment is,

The epoxy resin (A) is preferably contained in 100 mass% of the composition, preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass. It may be included in the following amount,

The curing agent (B) is preferably contained 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, more preferably 1.0% by mass or more and 7% by mass or less. It can be included in an amount of

The high dielectric constant filler (C) may be included in 30% by mass or more, preferably 35% by mass or more, more preferably 45% by mass or more, in 100% by mass of the composition. The upper limit is 80 mass%.

In the present embodiment, an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C) are contained in combination, and the high dielectric constant filler (C) is contained in an amount of 30% by mass or more in 100% by mass of the composition. By doing so, it is possible to provide a thermosetting resin composition that yields a dielectric substrate with superior high dielectric constant and low dielectric tangent.

The thermosetting resin composition of this embodiment can be manufactured by uniformly mixing each of the components described above. The manufacturing method includes sufficiently mixing a predetermined amount of raw materials with a mixer or the like, melting and kneading them with a mixing roll, kneader, or extruder, followed by cooling and pulverizing. If necessary, the obtained thermosetting resin composition may be tableted with a size and mass suitable for molding conditions.

The thermosetting resin composition of this embodiment has a spiral flow flow length of 70 cm or more, preferably 80 cm or more, more preferably 90 cm or more, and still more preferably 100 cm or more. Therefore, the thermosetting resin composition of this embodiment has excellent moldability.

For the spiral flow test, for example, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), pouring the mold into a mold for spiral flow measurement in accordance with EMMI-1-66 at a mold temperature of 175°C. This can be done by injecting the resin molding material under the conditions of a pressure of 6.9 MPa and a curing time of 120 seconds and measuring the flow length.

The gel time of the thermosetting resin composition of this embodiment is preferably 32 seconds or more and 80 seconds or less, and more preferably 35 seconds or more and 70 seconds or less.

By setting the gel time of the thermosetting resin composition to the above lower limit or more, the fillability is excellent, and by setting it to the above upper limit or less, the moldability becomes good.

Moreover, the thermosetting resin composition of this embodiment has a rectangular pressure measured under the following conditions of 0.1 MPa or more, preferably 0.15 MPa or more, and more preferably 0.20 MPa or more.

Rectangular pressure is a parameter of melt viscosity, and the smaller the value, the lower the melt viscosity. The thermosetting resin composition of the present embodiment has excellent mold filling properties during molding because the rectangular pressure is within the above range.

(condition)

Using a low-pressure transfer molding machine, the thermosetting resin composition is injected into a rectangular flow path with a width of 13 mm, a thickness of 1 mm, and a length of 175 mm under the conditions of a mold temperature of 175°C and an injection speed of 177 mm ³ /sec, and is placed at a position of 25 mm from the upstream end of the flow path. The change in pressure over time is measured with an embedded pressure sensor, the minimum pressure during flow of the thermosetting resin composition is calculated, and this minimum pressure is taken as the rectangular pressure.

The thermosetting resin composition of the present embodiment has the following dielectric constant and dielectric tangent (tanδ) in the cured product obtained by heating at 200°C for 90 minutes.

The dielectric constant at 25GHz using the cavity resonance technique can be set to 10 or more, preferably 12 or more, and more preferably 13 or more.

The dielectric tangent (tanδ) at 25GHz using the cavity resonance technique can be set to 0.04 or less, preferably 0.03 or less, more preferably 0.02 or less, and particularly preferably 0.015 or less.

The cured product obtained from the thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric tangent in the high frequency band, so it can achieve high frequency, shortening circuits, and miniaturization of communication devices, etc., and can be used as a microstrip antenna. It can be suitably used as a material that forms a material, a material that forms a dielectric waveguide, and a material that forms an electromagnetic wave absorber.

<Microstrip antenna>

Since the microstrip antenna of this embodiment has the structures shown in FIGS. 1 and 2 (a) and (b) in the same manner as the embodiment of the first invention, description is omitted.

<Dielectric waveguide>

In this embodiment, the dielectric waveguide includes a dielectric formed 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) and transmits them.

The conductor film can be made of a metal such as copper or an oxide high-temperature superconductor.

<Electromagnetic wave absorber>

In this embodiment, the electromagnetic wave absorber has a structure in which a support, a resistance film, a dielectric layer, and a reflection layer are laminated. The electromagnetic wave absorber can be used as a λ/4 type radio wave absorber with high radio wave absorption performance.

Examples of the support include a resin substrate. By using the support, the resistance film can be protected and durability as a radio wave absorber can be improved.

Examples of the resistance film include indium tin oxide and molybdenum-containing resistance film.

The dielectric layer is formed by curing the thermosetting resin composition of this embodiment. The thickness is approximately 10 μm or more and 2000 μm or less.

The reflective layer can function as a reflective layer for radio waves, and an example is a metal film.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted as long as they do not impair the effects of the present invention.

Example

Below, the present invention will be described in more detail through examples, but the present invention is not limited to these.

Examples related to the first invention (claims 1 to 13, 22 to 24 at the time of application) and the first embodiment are shown in Example A.

Examples related to the second invention (claims 14 to 21, 22 to 24 at the time of application) and the second embodiment are shown in Example B.

<Example A>

[Examples A1 to A4, Comparative Example A1]

<Preparation of thermosetting resin composition>

The following raw materials were mixed at the content shown in Table 1 using a mixer at room temperature, and then roll kneaded at 70 to 100°C. Next, after cooling the obtained kneaded material, it was pulverized to obtain a granular thermosetting resin composition. Next, tablet-shaped thermosetting resin composition was obtained by tableting and molding at high pressure.

Below, information on the raw materials in Table 1 is shown.

(High dielectric constant filler)

High dielectric constant filler 1: Calcium titanate (CT, average particle diameter 2.0 μm, manufactured by Fuji Titanium, relative dielectric constant at 25°C, 1 GHz: 135)

(Inorganic filler)

Inorganic filler 1: Alumina (K75-1V25F, manufactured by Denka Co., Ltd.)

Inorganic filler 2: Fused spherical silica (SC-2500-SQ, manufactured by Admatex)

(thermosetting resin)

Epoxy resin 1: Biphenyl type epoxy resin (YX-4000K, manufactured by Mitsubishi Chemical Corporation)

Epoxy resin 2: Phenol aralkyl type epoxy resin containing a biphenylene skeleton (NC3000L, manufactured by Nippon Kayaku Co., Ltd.)

Epoxy resin 3: Bisphenol A type epoxy resin (YL6810, manufactured by Mitsubishi Chemical Corporation)

(Active ester compound)

·Active ester compound 1: Active ester compound prepared by the following preparation method

279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer. was dissolved under reduced pressure by nitrogen substitution. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (number of moles of phenolic hydroxyl group: 1.33 mol) of dicyclopentadienephenol resin were added, and the system was dissolved by purging with reduced pressure nitrogen. After that, while purging nitrogen gas, the system was controlled to 60°C or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. Additionally, water was added to the toluene phase in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the liquid was left standing to remove the aqueous layer. This operation was repeated until the pH of the water layer reached 7. Afterwards, moisture was removed by decanter dehydration to obtain an activated ester resin in a toluene solution with a non-volatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it had a structure in which R ¹ and R ³ were hydrogen atoms, Z was a naphthyl group, and l was 0 in the above-mentioned formula (1-1). Additionally, the average value k of the repeating unit was calculated from the reaction equivalence ratio and was in the range of 0.5 to 1.0.

·Active ester compound 2: Active ester compound prepared by the following preparation method

203.0 g of 1,3-benzenedicarboxylic acid dichloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer, and the system was filled with reduced pressure nitrogen. It was dissolved by substitution. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (number of moles of phenolic hydroxyl group: 1.33 mol) of dicyclopentadienephenol resin were added, and the system was dissolved by purging with reduced pressure nitrogen. After that, while purging nitrogen gas, the system was controlled to 60°C or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. Additionally, water was added to the toluene phase in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the liquid was left standing to remove the aqueous layer. This operation was repeated until the pH of the water layer reached 7. Afterwards, moisture was removed by decanter dehydration to obtain an activated ester resin in a toluene solution with a non-volatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it had a structure in which R ¹ and R ³ were hydrogen atoms, Z was a naphthyl group, and l was 0 in the above-mentioned formula (1-3). The average value k of the repeating units of the activated ester resin was calculated from the reaction equivalence ratio and was in the range of 0.5 to 1.0. The obtained active ester resin had a structure specifically represented by the following chemical formula. In the formula below, the average value k of the repeating unit was 0.5 to 1.0.

(hardener)

· Phenol-based curing agent 1: Biphenyl aralkyl type resin (HE910-20, manufactured by Air/Water)

· Phenol-based curing agent 2: Phenol aralkyl type resin containing biphenylene skeleton (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)

(Silane coupling agent)

・Silane coupling agent 1: Phenylaminopropyltrimethoxysilane (CF4083, Toray Dow Corning Co., Ltd.)

・Silane coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sylar Ace, manufactured by JNC)

(curing catalyst)

Curing catalyst 1: tetraphenylphosphonium-4,4'-sulfonyldiphenolate

Curing catalyst 2: Tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate

(Lee Hyeong-je)

・Mold release agent 1: Glycerin trimonocarbonate ester (Recoluv WE-4, manufactured by Clariant Japan)

(Evaluation of dielectric constant and dielectric tangent using cavity resonance technique)

The obtained thermosetting resin composition was applied to a Si substrate, prebaked at 120°C for 4 minutes, and a resin film with a coating thickness of 12 μm was formed.

This was heated at 200°C for 90 minutes in a nitrogen atmosphere using an oven, and treated with hydrofluoric acid (immersed in a 2% by mass aqueous hydrofluoric acid solution). After removing the substrate from the hydrofluoric acid, the cured film was peeled from the Si substrate, and this was used as a test piece.

The measurement equipment used was a network analyzer HP8510C, a synthesized sweeper HP83651A, and a test set HP8517B (all manufactured by Agilent Technologies). These devices and a cylindrical cavity resonator (inner diameter 42 mm, height 30 mm) were set up.

The resonance frequency, 3 dB bandwidth, transmission power ratio, etc. were measured at a frequency of 18 GHz with and without the test piece inserted into the resonator. Then, the dielectric properties of dielectric constant (Dk) and dielectric tangent (Df) were obtained by analytically calculating these measurement results using software. Additionally, the measurement mode was set to TE ₀₁₁ mode.

(Glass transition temperature, coefficient of linear expansion)

The glass transition temperature (Tg) and coefficient of linear expansion (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 for encapsulation was injection molded at a mold temperature of 175°C, injection pressure of 6.9 MPa, and curing time of 120 seconds, and a 10 mm × 4 mm mold was formed. A test piece of ×4 mm was obtained. Next, the obtained test piece was post-cured at 175°C for 4 hours, and then measured using a thermomechanical analysis device (TMA100, manufactured by Seiko Denshi Kogyo Co., Ltd.) at a temperature range of 0°C to 320°C and a temperature increase rate of 5°C/min. It was measured under the conditions. From this measurement result, the glass transition temperature (Tg), the coefficient of linear expansion (CTE1) below the glass transition temperature, and the coefficient of linear expansion (CTE2) above the glass transition temperature were calculated.

(Evaluation of mechanical strength (bending strength, bending modulus))

The obtained thermosetting resin composition was injection molded into a mold 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. As a result, a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm was obtained. Next, the obtained molded article was post-cured at 175°C for 4 hours. In this way, a test piece for evaluation of mechanical strength was produced. Then, 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 at a head speed of 5 mm/min based on JIS K 6911.

[Table 1]

(Durability at ten)

The cured product of the obtained thermosetting resin composition was evaluated for the rate of change in physical properties after repeated 10 times of heat history at 175°C for 100 hours. When the bending elastic modulus at 260°C before the heat history before repetition is FMa, and the bending elastic modulus at 260°C before the heat history after repetition is FMb, the change rate obtained from (FMa-FMb)/FMa×100% is within 200%. It was evaluated as ○, and cases exceeding 200% were evaluated as ×.

The thermosetting resin compositions of Examples A1 to A4 according to the first invention are excellent in high dielectric constant and low dielectric tangent in the high frequency band, and can form a member (cured product) with excellent heat durability compared to Comparative Example A1. The results are shown.

Such thermosetting resin compositions can be appropriately used to form part of high-frequency devices such as microstrip antennas, dielectric waveguides, and multilayer antennas.

<Example B>

[Examples B1 to B10, Comparative Example B1]

The following raw materials were mixed in the mixing amounts shown in Table 2 using a mixer at room temperature, and then roll kneaded at 70 to 100°C. Next, after cooling the obtained kneaded material, it was pulverized to obtain a granular resin composition. Next, a tablet-like resin composition was obtained by tableting and molding at high pressure.

(High dielectric constant filler)

·High dielectric constant filler 1: Calcium titanate (average particle diameter 2.0μm)

(Inorganic filler)

Inorganic filler 1: Alumina (DAB25MA-TS3, manufactured by Denka Co., Ltd.)

Inorganic filler 2: Fused spherical silica (SC-2500-SQ, manufactured by Admatex)

(coloring agent)

Colorant 1: Black titanium oxide (manufactured by Ako Kasei)

(Coupling agent)

Coupling agent 1: Phenylaminopropyltrimethoxysilane (CF-4083, manufactured by Toray/Dow Corning)

Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sylar Ace, manufactured by JNC)

(epoxy resin)

Epoxy resin 1: Phenol aralkyl type epoxy resin containing a biphenylene skeleton (NC-3000L, manufactured by Nippon Kayaku Co., Ltd., containing a structural unit represented by the general formula (a) above)

(hardener)

Curing agent 1: Active ester-based curing agent prepared by the following preparation method

(Method for preparing activated ester-based hardener)

279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer. was dissolved under reduced pressure by nitrogen substitution. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (number of moles of phenolic hydroxyl group: 1.33 mol) of dicyclopentadienephenol resin were added, and the system was dissolved by purging with reduced pressure nitrogen. After that, while purging nitrogen gas, the system was controlled to 60°C or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. Additionally, water was added to the toluene phase in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the liquid was left standing to remove the aqueous layer. This operation was repeated until the pH of the water layer reached 7. Afterwards, moisture was removed by decanter dehydration to obtain an activated ester resin in a toluene solution with a non-volatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it had a structure in which R ¹ and R ³ were hydrogen atoms, Z was a naphthyl group, and l was 0 in the above-mentioned formula (1-1). Additionally, the average value k of the repeating unit was calculated from the reaction equivalence ratio and was in the range of 0.5 to 1.0.

Curing agent 2: Phenol aralkyl type resin containing biphenylene skeleton (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)

Curing agent 3: Phenol hydroxybenzaldehyde type curing agent (MEH-7500, manufactured by Meiwa Kasei Co., Ltd.)

Curing agent 4: Novolac type phenolic resin (Sumilite Resin PR-51470, manufactured by Sumitomo Bakelite)

Curing agent 5: Xylok-type phenol aralkyl-type phenol curing agent (MEHC-7800SS, manufactured by Meiwa Kasei Co., Ltd.)

Curing agent 6: Polyhydric MAR type phenol curing agent (SH-002-02, manufactured by Meiwa Kasei Co., Ltd.)

Curing agent 7: Active ester-based curing agent prepared by the following preparation method

(Method for preparing activated ester-based hardener)

203.0 g of 1,3-benzenedicarboxylic acid dichloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer, and the system was filled with reduced pressure nitrogen. It was dissolved by substitution. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (number of moles of phenolic hydroxyl group: 1.33 mol) of dicyclopentadienephenol resin were added, and the system was dissolved by purging with reduced pressure nitrogen. After that, while purging nitrogen gas, the system was controlled to 60°C or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. Additionally, water was added to the toluene phase in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the liquid was left standing to remove the aqueous layer. This operation was repeated until the pH of the water layer reached 7. Afterwards, moisture was removed by decanter dehydration to obtain an activated ester resin in a toluene solution with a non-volatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it had a structure in which R ¹ and R ³ were hydrogen atoms, Z was a naphthyl group, and l was 0 in the above-mentioned formula (1-3). The average value k of the repeating units of the activated ester resin was calculated from the reaction equivalence ratio and was in the range of 0.5 to 1.0. The obtained active ester resin had a structure specifically represented by the following chemical formula. In the formula below, the average value k of the repeating unit was 0.5 to 1.0.

(catalyst)

Catalyst 1: Tetraphenylphosphonium-4,4'-sulfonyldiphenolate

(Evaluation of dielectric constant and dielectric tangent using cavity resonance technique)

First, a test piece was obtained using the resin composition.

Specifically, the resin composition prepared in Examples and Comparative Examples was applied to a Si substrate and prebaked at 120°C for 4 minutes to form a resin film with a coating thickness of 12 μm.

This was heated at 200°C for 90 minutes in a nitrogen atmosphere using an oven, and treated with hydrofluoric acid (immersed in a 2% by mass aqueous hydrofluoric acid solution). After removing the substrate from the hydrofluoric acid, the cured film was peeled from the Si substrate, and this was used as a test piece.

The measurement equipment used was a network analyzer HP8510C, a synthesized sweeper HP83651A, and a test set HP8517B (all manufactured by Agilent Technologies). These devices and a cylindrical cavity resonator (inner diameter 42 mm, height 30 mm) were set up.

The resonance frequency, 3 dB bandwidth, transmission power ratio, etc. were measured at a frequency of 25 GHz with and without the test piece inserted into the resonator. Then, the dielectric properties of dielectric constant (Dk) and dielectric tangent (Df) were obtained by analytically calculating these measurement results using software. Additionally, the measurement mode was set to TE ₀₁₁ mode.

(Measurement of spiral flow)

Using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement conforming to EMMI-1-66 was placed with a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds. Under these conditions, the resin compositions obtained in Examples and Comparative Examples were injected, and the flow length was measured.

(Gel Time (GT))

The resin compositions of Examples and Comparative Examples were each melted on a hot plate heated to 175°C, kneaded with a spatula, and the time until hardening (unit: seconds) was measured.

(molding shrinkage rate)

For each Example and Comparative Example, it was assumed that the obtained resin composition was subjected to molding (ASM: as Mold) and then the molding shrinkage (after ASM) was measured, and after the molding, the dielectric substrate was produced by main curing. Mold shrinkage (after PMC) was evaluated under heating conditions (PMC: Post Mold Cure).

First, a test piece produced using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) under the conditions of a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds was tested in accordance with JIS K 6911. Molding shrinkage (after ASM) was obtained.

Additionally, the obtained test piece was heat treated at 175°C for 4 hours, and molding shrinkage (after ASM) was measured in accordance with JIS K 6911.

(Glass transition temperature, coefficient of linear expansion)

For each Example and Comparative Example, the glass transition temperature (Tg) and coefficient of linear expansion (CTE1, CTE2) of the cured product of the obtained resin composition were measured as follows. First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), the resin composition for encapsulation was injection molded at a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds to form a 10 mm × 4 mm × 10 mm × 4 mm mold. A test piece of 4 mm was obtained. Next, the obtained test piece was post-cured at 175°C for 4 hours, and then measured using a thermomechanical analysis device (TMA100, manufactured by Seiko Denshi Kogyo Co., Ltd.) at a temperature range of 0°C to 320°C and a temperature increase rate of 5°C/min. It was measured under the conditions. From this measurement result, the glass transition temperature (Tg), the coefficient of linear expansion (CTE1) below the glass transition temperature, and the coefficient of linear expansion (CTE2) above the glass transition temperature were calculated.

(Evaluation of mechanical strength (bending strength/bending modulus))

The resin compositions of the examples and comparative examples were injection molded into a mold 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. . As a result, a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm was obtained. Next, the obtained molded article was post-cured at 175°C for 4 hours. In this way, a test piece for evaluation of mechanical strength was produced. Then, 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 at a head speed of 5 mm/min based on JIS K 6911.

[Table 2]

From the results in Table 2, it became clear that, according to the thermosetting resin composition of the second invention, a dielectric substrate excellent in high dielectric constant and low dielectric tangent, in other words, excellent in the balance of these properties, was obtained. In addition, it became clear that the thermosetting resin composition of the present invention has excellent moldability in that the spiral flow flow length is long and the gel time is in an appropriate range.

This application is Japanese Patent Application No. 2021-051748 filed on March 25, 2021, Japanese Patent Application No. 2021-172197 filed on October 21, 2021, and Japanese Patent Application No. 2021-172197 filed on December 6, 2021. Japanese Patent Application No. 2021-197667, filed on December 6, 2021 Japanese Patent Application No. 2021-197669, filed on December 6, 2021 Japanese Patent Application No. 2021-197679, filed on December 6, 2021 Priority is claimed based on Japanese Patent Application No. 2021-197720 and Japanese Patent Application No. 2021-197731 filed on December 6, 2021, and the entire disclosures thereof are incorporated herein by reference.

10 microstrip antenna
12 Dielectric substrate
14 Radiating conductor plate
16 Map board
20, 20' microstrip antenna
22 Dielectric substrate
24 High dielectric substrate
26 spacer
a void part

Claims (24)

Thermosetting resin,
A high dielectric constant filler with a relative dielectric constant of 10 or more at 25°C and 25GHz,
A thermosetting resin composition comprising an active ester compound,
When the bending elastic modulus at 25°C, measured according to the following procedure, is FM ₂₅ and the bending elastic modulus at 260°C is FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ are 0.005 ≤ FM ₂₆₀ /FM ₂₅ ≤ A thermosetting resin composition that satisfies 0.1.
(sequence)
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 to obtain a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm.
The obtained molded article was post-cured at 175°C for 4 hours, and a test piece was produced.
The bending elastic modulus (N/mm ² ) of the test piece at room temperature (25°C) or 260°C is measured based on JIS K 6911. In claim 1,
When the bending strength at 25°C measured in accordance with JIS K 6911 according to the above procedure is FS ₂₅ and the bending strength at 260°C is FS ₂₆₀ , FS ₂₅ and FS ₂₆₀ are 0.025≤FS. A thermosetting resin composition that satisfies ₂₆₀ /FS ₂₅ ≤0.2. In claim 1 or claim 2,
A thermosetting resin composition wherein a cured product of the thermosetting resin composition has a glass transition temperature of 100°C or more and 250°C or less. The method according to any one of claims 1 to 3,
In the cured product of the thermosetting resin composition, the linear expansion coefficient CTE1 in the range below the glass transition temperature is 5 ppm/°C or more and 25 ppm/°C or less, and the linear expansion coefficient CTE2 in the range exceeding the glass transition temperature and 320°C or less is 30 ppm/°C or more. A thermosetting resin composition of 100ppm/℃ or less. The method according to any one of claims 1 to 4,
A thermosetting resin composition in which the high dielectric constant filler contains calcium titanate. The method according to any one of claims 1 to 5,
A thermosetting resin composition in which the content of the high dielectric constant filler is 30% by mass or more and 90% by mass or less based on 100% by mass of the thermosetting resin composition. The method according to any one of claims 1 to 6,
The active ester compound 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 acetylate of phenol novolak, and a benzoylate of phenol novolac. A thermosetting resin composition containing at least one type selected from active ester compounds containing. The method according to any one of claims 1 to 7,
A thermosetting resin composition in which the active ester compound has a structure represented by the following general formula (1).

(In the above general formula (1),
A is a substituted or unsubstituted arylene group connected through an aliphatic cyclic hydrocarbon group,
Ar' is a substituted or unsubstituted aryl group,
B is a structure represented by the following general formula (B),

(In General Formula (B), Ar is a substituted or unsubstituted arylene group, and Y is a single bond, a substituted or unsubstituted straight-chain alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 3 carbon atoms. (~6 cyclic alkylene group, substituted or unsubstituted divalent aromatic hydrocarbon group, ether bond, carbonyl group, carbonyloxy group, sulfide group, or sulfone group. n is an integer of 0 to 4.)
k is the average value of the repetition unit and ranges from 0.25 to 3.5.) The method according to any one of claims 1 to 8,
A thermosetting resin composition in which the thermosetting resin contains an epoxy resin containing a biphenylene skeleton. The method according to any one of claims 1 to 9,
A thermosetting resin composition further comprising a phenol-based curing agent. In claim 10,
A thermosetting resin composition in which the phenol-based curing agent contains a phenol resin containing a biphenylene skeleton. The method according to any one of claims 1 to 11,
A thermosetting resin composition used to form part of a high-frequency device selected from the group consisting of microstrip antennas, dielectric waveguides, and multilayer antennas. A high-frequency device comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 12. (A) epoxy resin,
(B) a curing agent,
(C) A thermosetting resin composition comprising a high dielectric constant filler,
The epoxy resin (A) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin (excluding the biphenyl aralkyl type epoxy resin),
The curing agent (B) includes an active ester-based curing agent and a phenol-based curing agent,
The high dielectric constant filler (C) is calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, and titanate. Contains at least one selected from calcium zirconate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate,
A thermosetting resin composition comprising a high dielectric constant filler (C) in an amount of 30% by mass or more in 100% by mass of the thermosetting resin composition. In claim 14,
A thermosetting resin composition wherein the high dielectric constant filler (C) is at least one selected from calcium titanate, strontium titanate, and magnesium titanate. In claim 14 or claim 15,
The active ester-based curing agent includes an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylate of phenol novolak, and phenol A thermosetting resin composition that is at least one selected from active ester-based curing agents containing the benzoylate of novolak. The method of any one of claims 14 to 16,
The active ester-based curing agent is a thermosetting resin composition having a structure represented by the following general formula (1).

(In General Formula (1), A is a substituted or unsubstituted arylene group connected through an aliphatic cyclic hydrocarbon group, Ar' is a substituted or unsubstituted aryl group,
B is a structure represented by the following general formula (B),

(In General Formula (B), Ar is a substituted or unsubstituted arylene group, and Y is a single bond, a substituted or unsubstituted straight-chain alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 3 carbon atoms. (~6 cyclic alkylene group, substituted or unsubstituted divalent aromatic hydrocarbon group, ether bond, carbonyl group, carbonyloxy group, sulfide group, or sulfone group. n is an integer of 0 to 4.)
k is the average value of the repetition unit and ranges from 0.25 to 3.5.) The method of any one of claims 14 to 17,
A thermosetting resin composition further comprising a curing catalyst (D). The method according to any one of claims 14 to 18,
A thermosetting resin composition used as a material for forming a microstrip antenna. The method according to any one of claims 14 to 18,
A thermosetting resin composition used as a material for forming a dielectric waveguide. The method according to any one of claims 14 to 18,
A thermosetting resin composition used as a material for forming an electromagnetic wave absorber. A dielectric substrate obtained by curing the thermosetting resin composition according to any one of claims 1 to 12 and 14 to 21. A dielectric substrate according to claim 22,
a radiation conductor plate provided on one side of the dielectric substrate;
A microstrip antenna comprising a conductor plate provided on the other side of the dielectric substrate. a dielectric substrate,
a radiation conductor plate provided on one side of the dielectric substrate;
a conductive plate provided on the other side of the dielectric substrate;
A microstrip antenna comprising a high dielectric material disposed opposite to the radiation conductor plate,
A microstrip antenna wherein the high dielectric constant is constituted by the dielectric substrate according to claim 22.

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