JP2024014929A - Thermosetting resin compositions, high frequency devices, dielectric substrates, and microstrip antennas - Google Patents

Abstract

An object of the present invention is to provide a thermosetting resin composition capable of forming a member excellent in high dielectric constant, low dielectric loss tangent, etc., and a high frequency device using the same. [Solution] The thermosetting resin composition of the present invention contains a thermosetting resin, a high dielectric constant filler having a dielectric constant of 10 or more at 25° C. and 25 GHz, and an active ester compound. FM25 and FM260 satisfy 0.005≦FM260/FM25≦0.1. It is composed of Further, 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 of a biphenylaralkyl type. Contains an epoxy resin and/or a biphenyl type epoxy resin (excluding biphenylaralkyl type epoxy resin), the curing agent (B) contains an active ester curing agent and a phenolic curing agent, and the 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, calcium zirconate titanate, zircon titanate The thermosetting resin composition contains at least one selected from lead acid, barium magnesium niobate, and calcium zirconate, and contains 30% by mass or more of the high dielectric constant filler (C) in 100% by mass of the thermosetting resin composition. Included in quantity. [Selection diagram] None

Description

The present invention relates to a thermosetting resin composition, a high frequency device, a dielectric substrate, and a microstrip antenna.

In recent years, wireless communication has become faster, and there is a demand for higher performance and smaller size of the communication equipment used. Furthermore, in recent years, the capacity of wireless communication has increased rapidly, and as a result, the frequencies used for transmission signals are rapidly becoming wider and higher in frequency. For this reason, the frequency band used by communication equipment cannot be supported by the conventional microwave band alone, and is being expanded to include the millimeter wave band. Against this background, there is a strong demand for higher performance antennas installed in communication equipment.

Communication equipment can be further miniaturized if the dielectric constant of the antenna material (dielectric substrate) built into the communication equipment increases. Furthermore, when the dielectric loss tangent of the dielectric substrate becomes smaller, the loss becomes lower, which is advantageous for higher frequencies. Therefore, if a dielectric substrate with a high dielectric constant and a small dielectric loss tangent can be used, it is possible to achieve higher frequencies, thereby shortening the circuit length and downsizing the communication equipment.

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

Patent Document 2 discloses a resin composition that includes a siloxane-modified polyamideimide resin, a high dielectric constant filler, and an epoxy resin, and has a cured product having a dielectric constant of 15 or more at 25° C. and 1 MHz. Examples of this document describe an example in which barium titanate is used as the high dielectric constant filler.

Patent Document 3 discloses a resin composition containing an epoxy resin, a dielectric powder, a nonionic surfactant, and an active ester curing agent. This document states that this resin composition can be used as a high dielectric constant insulating material for electronic components used in a high frequency region and a high dielectric constant insulating material for fingerprint sensors. The example of this document describes an example in which barium titanate is used as the dielectric powder.

Patent Document 4 includes an epoxy resin, a curing agent, and an inorganic filler containing predetermined amounts of calcium titanate particles and strontium titanate particles, the inorganic filler consisting of silica particles and alumina particles. Disclosed is a molding resin composition which further contains at least one member selected from the group consisting of:

JP 2018-41998 Publication Japanese Patent Application Publication No. 2004-315653 JP 2020-105523 Publication Patent No. 6870778

However, the conventional techniques described in Patent Documents 1 to 4 have room for improvement in the following points.
It has been found that there is room for improvement in the composite material described in Patent Document 1 above in terms of high dielectric constant and low dielectric loss tangent in higher frequency bands, and also in terms of thermal durability. This should be the first issue.
Further, the dielectric substrates described in Patent Documents 1 to 4 mentioned above have problems with high dielectric constants and low dielectric loss tangents, and these problems are particularly noticeable in high frequency bands. This is the second issue.

The present inventors have solved the above problem by controlling the ratio of flexural modulus at 260°C to 25°C within an appropriate range by using a high dielectric constant filler and an active ester compound together in a thermosetting resin composition. He discovered that the first problem could be solved 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 25 GHz,
an active ester compound;
A thermosetting resin composition comprising,
When the flexural modulus at 25°C is FM ₂₅ and the flexural modulus at 260°C is FM ₂₆₀ , measured according to the procedure below, FM ₂₅ and FM ₂₆₀ are 0.005≦FM ₂₆₀ /FM ₂₅ ≦0 .1 is satisfied.
A thermosetting resin composition is provided.
(procedure)
The thermosetting resin composition was injection-molded into a mold using a low-pressure transfer molding machine under the conditions of a mold temperature of 130°C, an injection pressure of 9.8 MPa, and a curing time of 300 seconds. A molded product with a length of 80 mm is obtained.
The obtained molded product is post-cured at 175° C. for 4 hours to prepare a test piece.
The flexural modulus (N/mm ² ) of the test piece at room temperature (25° C.) or 260° C. is measured in accordance with JIS K 6911.

Further, according to the first invention,
A high frequency device is provided that includes a cured product of the above thermosetting resin composition.

Furthermore, the present inventors have discovered that the above second problem can be solved by a combination of specific components, and have completed the second invention.
That is, the second invention can be shown below.
According to the second invention, (A) an epoxy resin;
(B) a curing agent;
(C) a high dielectric constant filler;
A thermosetting resin composition comprising,
The epoxy resin (A) contains a biphenylaralkyl-type epoxy resin and/or a biphenyl-type epoxy resin (excluding a biphenylaralkyl-type epoxy resin),
The curing agent (B) contains an active ester curing agent and a phenolic 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, The thermosetting resin composition contains at least one selected from calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate, and contains a high dielectric constant filler in 100% by mass of the thermosetting resin composition. A thermosetting resin composition containing (C) in an amount of 30% by mass or more can be provided.

According to the second invention,
A dielectric substrate obtained 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 surface of the dielectric substrate;
a ground conductor plate provided on the other surface of the dielectric substrate;
A microstrip antenna is provided.

According to the first or second invention,
A dielectric substrate,
a radiation conductor plate provided on one surface of the dielectric substrate;
a ground conductor plate provided on the other surface of the dielectric substrate;
a high dielectric material disposed opposite to the radiation conductor plate;
A microstrip antenna comprising:
A microstrip antenna is provided, wherein the high dielectric material 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 having a high dielectric constant, a low dielectric loss tangent, and excellent durability under heat, and a high frequency device using the same.
Further, according to the second invention, a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent is obtained, and a thermosetting resin composition with excellent moldability, and a dielectric substrate made of the resin composition, And a microstrip antenna including 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 loss tangent.

FIG. 2 is a top perspective view showing the microstrip antenna of this embodiment. FIG. 3 is a cross-sectional view showing another aspect of the microstrip antenna of this embodiment.

Hereinafter, the first invention (claims 1 to 13 as filed and claims 22 to 24 as filed) will be explained based on the first embodiment with reference to the drawings, and the second invention (claims 14 to 21 as filed) will be explained based on the first embodiment with reference to the drawings. , 22 to 24) will be explained based on the second embodiment with reference to the drawings.
Note that in all the drawings, similar components are denoted by the same reference numerals, and descriptions thereof will be omitted as appropriate. Further, for example, "1 to 10" represents "1 or more" to "10 or less" unless otherwise specified.

[First invention]
An overview of the thermosetting resin composition of the first embodiment will be explained.

The thermosetting resin composition of this embodiment includes a thermosetting resin, a high dielectric constant filler having a dielectric constant of 10 or more at 25° C. and 25 GHz, and an active ester compound, and was measured according to the following procedure. When the flexural modulus at 25°C is FM ₂₅ and the flexural modulus at 260°C is FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ should satisfy 0.005≦FM ₂₆₀ /FM ₂₅ ≦0.1. It is composed of

The lower limit of FM ₂₆₀ /FM ₂₅ is 0.005 or more, preferably 0.006 or more, more preferably 0.007 or more, still more preferably 0.008 or more. As a result, a member (cured product of a thermosetting resin composition) having a high dielectric constant and a low dielectric loss tangent can have good durability under heat.
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, still more preferably 0.02 or less. Thereby, the physical properties of the cured product of the thermosetting resin composition can be balanced.

Currently, due to design factors such as higher frequencies, higher output power of power semiconductors, and lower profile devices, the temperature of the operating environment tends to increase more and more. In order to cope with such an increase in the temperature of the operating environment, the inventors investigated the thermal characteristics of a cured product of a thermosetting resin composition.
According to the findings of the present inventors, the index FM ₂₆₀ /FM ₂₅ described above can stably evaluate the resistance to deformation before and after heat treatment of a cured product of a thermosetting resin composition. By setting the index FM ₂₆₀ /FM ₂₅ to the above lower limit value or more, it is possible to suppress thermal deterioration of the cured product due to heating, thereby improving the heat durability of the member formed using the cured product. It turns out that it can be improved.
Further, in the above member, it can be expected that deterioration of dielectric properties due to thermal deterioration will be suppressed.

In this embodiment, for example, by appropriately selecting the type and amount of each component contained in the thermosetting resin composition, the method for preparing the thermosetting resin composition, etc., the above-mentioned FM ₂₆₀ /FM ₂₅ , It is possible to control the following FS ₂₆₀ /FS ₂₅ , glass transition temperature, and linear expansion coefficient. Among these, for example, the use of calcium titanate as a high dielectric constant filler, the content of a high dielectric constant filler, the additional use of alumina as an inorganic filler, biphenyl type epoxy resin and/or as a thermosetting resin. A biphenylene skeleton-containing phenol aralkyl type epoxy resin and an active ester compound containing a dicyclopentadiene type diphenol structure are used together as an active ester compound, and a biphenylaralkyl type resin and/or a biphenylene skeleton containing phenol aralkyl type resin is used as a phenolic curing agent. Resins and the like are mentioned as elements for setting the above FM ₂₆₀ /FM ₂₅ , the following FS ₂₆₀ /FS ₂₅ , glass transition temperature, and coefficient of linear expansion within desired numerical ranges.

In addition, the thermosetting resin composition has a bending strength of FS ₂₅ at 25°C and a bending strength of FS 260 at 260°C, measured at a head speed of 5 mm/min according to JIS K ₆₉₁₁ according to the above procedure. In this case, 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, even more preferably 0.032 or more. Thereby, a member (cured product of a thermosetting resin composition) having a high dielectric constant and a low dielectric loss tangent can 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, still more preferably 0.05 or less. Thereby, the physical properties of the cured product of the thermosetting resin composition can be balanced.

(Measurement procedure for bending modulus and bending strength)
The thermosetting resin composition was injection-molded into a mold using a low-pressure transfer molding machine under the conditions of a mold temperature of 130°C, an injection pressure of 9.8 MPa, and a curing time of 300 seconds. A molded article of 80 mm is obtained.
The obtained molded product is post-cured at 175° C. for 4 hours to prepare a test piece.
In accordance with JIS K 6911, the flexural modulus (N/mm 2 ) and flexural strength (N/mm ² ) of the test piece were measured at room temperature (25°C) and 260°C at a head speed of 5 mm/min, ^respectively . Measure.

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 of 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 coefficient of linear expansion in the range below the glass transition temperature is defined as CTE1, and the coefficient of linear expansion in the range above the glass transition temperature and below 320°C is defined as 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.

Each component of the thermosetting resin composition of this embodiment will be described in detail below.

.
[Thermosetting resin]
The thermosetting resin composition of this embodiment contains a thermosetting resin.
As the thermosetting resin, one or more selected from epoxy resins, cyanate resins, and maleimide resins can be used. Among these, epoxy resins may be used.

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

Epoxy resins include, for example, biphenyl type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and tetramethylbisphenol F type epoxy resin; stilbene type epoxy resin; phenol novolac type epoxy resin, cresol novolac type Novolak type epoxy resins such as epoxy resins; polyfunctional epoxy resins such as trisphenol type epoxy resins such as triphenolmethane type epoxy resins and alkyl-modified triphenolmethane type epoxy resins; phenol aralkyl type epoxy resins having a phenylene skeleton , phenol aralkyl epoxy resins such as naphthol aralkyl epoxy resins having a phenylene skeleton, phenol aralkyl epoxy resins having a biphenylene skeleton, naphthol aralkyl epoxy resins having a biphenylene skeleton; epoxy resins containing a biphenylene skeleton; dihydroxynaphthalene epoxy resins , naphthol type epoxy resins such as epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimer; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene-modified phenol type epoxy resins Examples include bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as. These may be used alone or in combination of two or more.

Among these, epoxy resins containing a biphenylene skeleton are preferred, and it is more preferred to contain one or more selected from the group consisting of biphenylaralkyl-type epoxy resins and biphenyl-type epoxy resins (excluding biphenylaralkyl-type epoxy resins).

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.
Further, the content of the epoxy resin can 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, titanium Examples include lead acid zirconate, barium magnesium niobate, and calcium zirconate, and one or more selected from these can be used.

Among the above examples, the high dielectric constant filler may include at least one of calcium titanate and strontium titanate, and preferably includes calcium titanate. Thereby, the dielectric loss 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 even more preferably 0.5 μm or more and 10 μm or less.

The shape of the high dielectric constant filler is granular, amorphous, flake, etc., and high dielectric constant fillers having these shapes can be used in any ratio.

The content of the high dielectric constant filler is preferably 30% to 90% by mass, more preferably 35% to 80% by mass, even more preferably 40% to 70% by mass based on 100% by mass of the thermosetting resin composition. % range. When the amount of the high dielectric constant filler added is within the above range, the dielectric constant of the resulting cured product will be lower, and the production of molded products will also be 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 these, active ester compounds include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferred.

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 acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak. Examples include ester compounds. The active ester compound can contain at least one selected from these.
Among these, 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, for example, a resin having a structure represented by the following general formula (1) can be used as the active ester compound.

In formula (1), "B" is a structure represented by formula (B).

In formula (B), Ar is a substituted or unsubstituted arylene group. Examples of the 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, an aralkyl group, and the like.
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, ether bond, carbonyl group, carbonyloxy group, sulfide group, or sulfone group. Examples of the substituent of 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, an aralkyl group, and the like.
Preferred examples of Y include a single bond, a methylene group, -CH(CH ₃ ) ₂ -, an ether bond, an optionally substituted cycloalkylene group, and an optionally substituted 9,9-fluorenylene group.
n is an integer from 0 to 4, preferably 0 or 1.
Specifically, B is a structure represented by the following general formula (B1) or the following general formula (B2).

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

A is a substituted or unsubstituted arylene group connected via an aliphatic cyclic hydrocarbon group,
Ar' is a substituted or unsubstituted aryl group,
k is the average value of repeating units and ranges from 0.25 to 3.5.

Since the thermosetting resin composition of this embodiment contains a specific active ester compound, the obtained cured product can have excellent dielectric properties and is excellent in low dielectric loss 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 the epoxy resin and the active ester compound, the active ester group of the active ester compound reacts with the epoxy group of the epoxy resin to generate a secondary hydroxyl group. This secondary hydroxyl group is blocked by the ester residue of the active ester compound. Therefore, the dielectric loss tangent of the cured product is reduced.

In one embodiment, the structure represented by the above 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 an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether a bond, a carbonyl group, 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.

The structures represented by the above formulas (B-1) to (B-6) are all highly oriented structures, so when an active ester compound containing them is used, the resulting thermosetting resin composition The cured product can have a low dielectric loss tangent in a high frequency band.
Among them, from the viewpoint of low dielectric loss tangent, active ester compounds having a structure represented by formula (B-2), formula (B-3) or formula (B-5) are preferable, and furthermore, active ester compounds having a structure represented by formula (B-2), formula (B-3) or formula (B-5) are preferable. An active ester compound having a structure in which n is 0, a structure in which X in formula (B-3) is an ether bond, or a structure in which two carbonyloxy groups are at the 4,4'-position in formula (B-5) is more preferable. Further, 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 these, 1-naphthyl group or 2-naphthyl group is preferable because a cured product with a particularly low dielectric loss tangent can be obtained.

In this embodiment, [A] in the active ester compound represented by formula (1) is a substituted or unsubstituted arylene group connected via an aliphatic cyclic hydrocarbon group, and as such an arylene group, Examples of the structure include a structure obtained by polyaddition reaction between an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule and a phenolic compound.

Examples of the unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule include dicyclopentadiene, cyclopentadiene polymer, tetrahydroindene, 4-vinylcyclohexene, and 5-vinyl-2-norbornene. , limonene, etc., and each of these may be used alone or two or more types may be used in combination. Among these, dicyclopentadiene is preferred because it provides a cured product with excellent heat resistance. Since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain cyclopentadiene polymers and other aliphatic or aromatic diene compounds as impurities. However, in consideration of performance such as heat resistance, curability, and moldability, it is desirable to use a product with dicyclopentadiene purity of 90% by mass or more.

On the other hand, the phenolic compounds include, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, Examples include 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc., and each may be used alone or 2 More than one type may be used in combination. Among these, phenol is preferred because it forms an active ester compound with high curability and excellent dielectric properties in a 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 loss tangent in a high frequency band.

In formula (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 formula (1), more preferred are resins represented by the following formulas (1-1), (1-2), and (1-3), particularly Preferred examples include resins represented by the following formula (1-3).

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

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

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

The active ester compound represented by the above general formula (A) consists of a phenolic compound (a) having a structure in which a plurality of aryl groups having a phenolic hydroxyl group are linked via an aliphatic cyclic hydrocarbon group, and an aromatic nucleus-containing It can be produced by a known method of reacting a dicarboxylic acid or its halide (b) with an aromatic monohydroxy compound (c).

The reaction ratio of the phenolic compound (a), the aromatic nucleus-containing dicarboxylic acid or its halide (b), and the aromatic monohydroxy compound (c) can be adjusted as appropriate depending on the desired molecular design. Among them, since an active ester compound with higher curability can be obtained, the phenolic compound (a) is The phenolic hydroxyl group possessed by the aromatic monohydroxy compound (c) is in the range of 0.25 to 0.90 mol, and the hydroxyl group possessed by the aromatic monohydroxy compound (c) is in the range of 0.10 to 0.75 mol. It is preferable that the phenolic hydroxyl group of the phenolic compound (a) is in the range of 0.50 to 0.75 mol, and the hydroxyl group of the aromatic monohydroxy compound (c) is 0.25 mol. It is more preferable to use each raw material in a proportion ranging from 0.50 mol to 0.50 mol.

In addition, the functional group equivalent of the active ester compound is determined by the fact that a cured product with excellent curability and a low dielectric loss tangent can be obtained when the total number of aryl carbonyloxy groups and phenolic hydroxyl groups in the resin structure is taken as the number of functional groups in the resin. Therefore, it is preferably in the range of 200 g/eq or more and 230 g/eq or less, and more preferably in the range of 210 g/eq or more and 220 g/eq or less.

In the thermosetting resin composition of this embodiment, the content of the active ester compound and the epoxy resin is determined so that a cured product with excellent curability and a low dielectric loss tangent can be obtained. The ratio of epoxy groups in the epoxy resin to 1 equivalent is preferably 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 preferably accounts for 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, even more preferably 2% by mass or more and 9% by mass, based on 100% by mass of the thermosetting resin composition. % or less.
By containing the specific active ester compound within the above range, the obtained cured product can have better dielectric properties and is further excellent in low dielectric loss tangent.

By using the active ester compound and the above-mentioned high dielectric constant filler in combination, the thermosetting resin composition of this embodiment has excellent high dielectric constant and low dielectric loss tangent, and has excellent effects even in high frequency bands. .
From the viewpoint of the above effects, the active ester compound 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, even more preferably It can be included in an amount of 3 parts by mass or more and 15 parts by mass or less.

[Curing agent]
The thermosetting resin composition of this embodiment can contain a curing agent other than the active ester compound.
As other curing agents, phenolic curing agents, amine compound curing agents, amide compound curing agents, acid anhydride curing agents, etc. are used. These may be used alone or in combination of two or more. Among these, phenolic curing agents may be used.

Examples of the phenolic curing agent include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol resin containing a biphenylene skeleton, phenol aralkyl resin, naphthol aralkyl resin, and Methylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked with bismethylene groups), Examples of polyhydric phenol compounds include biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenolic nuclei are linked by bismethylene groups) and aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenolic nuclei are linked by melamine, benzoguanamine, etc.). It will be done.
Among these, biphenylaralkyl type phenol resins can be used.

Examples of the amine compound curing agent include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives.
Examples of the amide compound curing agent include polyamide resins synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine.
Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl Hexahydrophthalic anhydride is mentioned.

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

[Curing catalyst]
The thermosetting resin composition may also include a curing catalyst.
A curing catalyst is sometimes called a curing accelerator. The curing catalyst is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and any 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; 2-methylimidazole, 2- Imidazole such as phenylimidazole (imidazole curing accelerator); 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, etc. are examples of amidine and tertiary amine; quaternary of amidine and amine; Nitrogen atom-containing compounds such as salts can be mentioned, and only one type may be used, or two or more types may be used.

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 compounds containing phosphorus atoms, such as tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphine compounds and quinone compounds. It is more preferable to include compounds with latent properties such as adducts between phosphonium compounds and silane compounds, tetra-substituted phosphonium compounds, adducts between phosphine compounds and quinone compounds, and adducts between phosphonium compounds and silane compounds. Adducts are particularly preferred.

By using the compound (C) represented by the general formula (1) in combination with a curing catalyst having latent properties, it is possible to obtain a magnetic material with excellent formability and mechanical strength such as bending strength. .

Examples of the organic phosphine include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.

When a curing catalyst is used, its content is preferably 0.05 to 3% by mass, more preferably 0.08 to 2% by mass based on 100% by mass of the thermosetting resin composition. By setting the value within such a numerical range, a sufficient curing accelerating effect can be obtained without excessively deteriorating other performances.

[Inorganic filler]
The thermosetting resin composition of the present embodiment may further contain an inorganic filler in addition to the high dielectric constant filler in order to reduce hygroscopicity, reduce the coefficient of linear expansion, 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 made of spherical powders, and glass fibers. These inorganic fillers may be used alone or in combination of two or more. Among the above inorganic fillers, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity, and the shape of the filler is spherical from the viewpoint of fluidity during molding and mold abrasion resistance. is preferred.

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

[Other ingredients]
In addition to the above-mentioned components, the thermosetting resin composition of the present embodiment may contain various components such as a silane coupling agent, a mold release agent, a coloring agent, a dispersant, and a stress reducing agent, as necessary. can.
In particular, examples of the silane coupling agent include an amino group-containing silane coupling agent, a mercapto group-containing silane coupling agent, and the like. In addition, from the viewpoint of homogeneous mixing of the high dielectric constant filler and inorganic filler, the miscibility of the high dielectric constant filler with organic components such as epoxy resin, and the viewpoints of bending strength and bending elastic modulus, two types of these were selected. It is preferable to use the above.

[Thermosetting resin composition]
The thermosetting resin composition of this embodiment can be manufactured by uniformly mixing the above-mentioned components. Examples of the manufacturing method include a method in which raw materials having a predetermined content are thoroughly mixed using a mixer or the like, then melt-kneaded using a mixing roll, kneader, extruder, etc., followed by cooling and pulverizing. The obtained thermosetting resin composition may be made into tablets with a size and mass suitable for molding conditions, if necessary.

The cured product obtained from the thermosetting resin composition of the present embodiment has a high dielectric constant and a low dielectric loss tangent in a high frequency band, so it can be used for high frequencies and, therefore, for shortening circuits and miniaturizing high frequency devices such as communication equipment. can be achieved.

Such thermosetting resin compositions 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.
An example of a high frequency device will be described below.

<Microstrip antenna>
As shown in FIG. 1, the microstrip antenna 10 includes a dielectric substrate 12 formed by curing the above-mentioned thermosetting resin composition, and a radiation conductor plate (radiating element) provided on one surface of the dielectric substrate 12. ) 14, and a ground conductor plate 16 provided on the other surface of the dielectric substrate 12.

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

The radiation conductor plate 14 includes any one of a metal material, an alloy of metal materials, a cured product of 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, titanium, and the like. Alloys include multiple metallic materials. The metal paste agent includes one obtained by kneading a powder of a metal material 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 polymers, polyacetylene polymers, polyaniline polymers, polypyrrole polymers, and the like.

As shown in FIG. 1, the microstrip antenna 10 of this embodiment has a radiation conductor plate 14 with a length L and a width W, and resonates at a frequency where L corresponds to an integral multiple of 1/2 wavelength. . 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 ground conductor plate 16 is a thin plate made of a highly conductive metal such as copper, silver, or gold. The thickness may be sufficiently thin relative to the center operating frequency of the antenna device, and may be about 1/50th to 1/1000th wavelength of the center operating frequency.

Power feeding methods for microstrip antennas include direct feeding methods such as back coaxial feeding and coplanar feeding, and electromagnetic coupling feeding methods such as slot coupled feeding and proximity coupled feeding.

In the rear coaxial power feeding, power can be fed from the back surface of the antenna to the radiation conductor plate 14 using a coaxial line or a connector that penetrates the ground conductor plate 16 and the dielectric substrate 12.
In coplanar power feeding, power can be fed to the radiation conductor plate 14 using a microstrip line (not shown) arranged on the same plane as the radiation conductor plate 14.

In the slot coupled power supply, another dielectric substrate (not shown) is provided to sandwich the ground conductor plate 16, and the radiation conductor plate 14 and the microstrip line are formed on separate dielectric substrates. The radiation conductor plate 14 is excited by electromagnetically coupling the radiation conductor plate 14 and the microstrip line through the slots formed in the ground conductor plate 16.

In the close-coupled power supply, the dielectric substrate 12 has a laminated structure, and includes a dielectric substrate on which the radiation conductor plate 14 is formed, and a dielectric substrate on which the strip conductor of the microstrip line and the ground conductor plate 16 are arranged. It is layered. The radiation conductor plate 14 is excited by extending the strip conductor of the microstrip line below the radiation conductor plate 14 and electromagnetically coupling the radiation conductor plate 14 and the microstrip line.

FIGS. 2(a) and 2(b) show other embodiments of the microstrip antenna. Note that the same components as those in FIG. 1 are given the same numbers, and description thereof will be omitted as appropriate.
As shown in FIG. 2(a), the microstrip antenna 20 includes a dielectric substrate 22, a radiation conductor plate 14 provided on one surface of the dielectric substrate 22, and a radiation conductor plate 14 provided on the other surface of the dielectric substrate 22. The radiation conductor plate 16 includes a ground conductor plate 16 , 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 separated by a predetermined distance via 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 constituted by a dielectric substrate formed by curing the above-mentioned resin composition.
The gap between the dielectric substrate 22 and the high dielectric substrate 24 may be a space, or may be filled with a dielectric material.
Alternatively, as shown in a microstrip antenna 20' in FIG. 2(b), a structure may be adopted 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 conductive 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 metal such as copper, oxide high temperature superconductor, or the like.

<Multilayer antenna>
In this embodiment, the multilayer antenna includes a dielectric sheet formed by curing the thermosetting resin composition of this embodiment.
Specifically, a multilayer antenna is a module in which a circuit including a large number of elements such as capacitors and inductors is printed and stacked on dielectric sheets.

[Second invention]
The thermosetting resin composition of the second embodiment contains an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C), and contains a high dielectric constant filler (C) in 100% by mass of the composition. Contains 30% by mass or more of a dielectric constant filler (C).

[Epoxy resin (A)]
In the present embodiment, the epoxy resin (A) includes a biphenylaralkyl epoxy resin and/or a biphenyl epoxy resin (excluding the biphenylaralkyl epoxy resin).

The biphenylaralkyl epoxy resin of this embodiment preferably has a structural unit represented by the following general formula (a).

In general formula (a),
R ^a and R ^b are each independently a monovalent organic group, a hydroxyl group, or a halogen atom, if there are two or more,
r and s are each independently from 0 to 4;
* indicates that it is connected to another atomic group.

Specific examples of monovalent organic groups for R ^a and R ^b include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples include groups.

Examples of the alkyl group 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, heptyl group, Examples include octyl group, nonyl group, and decyl group.
Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
Examples of the alkynyl group include ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include tolyl group, xylyl group, phenyl group, naphthyl group, and anthracenyl group.
Examples of the aralkyl group include benzyl group and phenethyl group.
Examples of the alkaryl group include tolyl group and xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a 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, and neopentyloxy group. , n-hexyloxy group, etc.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

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

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

R ^c is each independently a monovalent organic group, a hydroxyl group, or a halogen atom when there is a plurality of them;
t is an integer from 0 to 3.
Specific examples of the monovalent organic group for R ^c include those listed as specific examples for R ^a and R ^b .
t is preferably 0-2, more preferably 0-1.

The weight average molecular weight Mw of the biphenylaralkyl epoxy resin of the present embodiment is preferably 500 or more and 2000 or less, more preferably 600 or more and 1900 or less, and even more preferably 700 or more and 1800 or less.

Further, the dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the biphenylaralkyl 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 even 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 homogeneous, which is preferable.

For weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn), polystyrene equivalent values obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement are used, for example. The measurement conditions for the GPC measurement are, for example, as follows.
Tosoh gel permeation chromatography device HLC-8320GPC
Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation
Detector: RI detector for liquid chromatogram Measurement temperature: 40°C
Solvent: THF
Sample concentration: 2.0mg/ml

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

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

Specifically, the biphenyl type epoxy resin includes diglycidyl ether of 4,4'-dihydroxybiphenyl, diglycidyl ether of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 3, Examples include diglycidyl ether of 3',5,5'-tetratert-butyl-4,4'-dihydroxybiphenyl, diglycidyl ether of dimethyldipropylbiphenol, and diglycidyl ether of dimethylbiphenol.

In addition to the above two types of epoxy resins, the epoxy resin (A) can also contain other epoxy resins as long as the effects of the present invention are not impaired.
Examples of other epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol aralkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, glycidylamine epoxy resins, and the like.

In this embodiment, the content of "biphenylaralkyl epoxy resin and/or biphenyl 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% by mass or less. It is not more than 80% by mass and not more than 100% by mass, and the epoxy resin (A) may contain only these two types of epoxy resins.

From the viewpoint of the effects of the present invention, the thermosetting resin composition (100% by mass) of the present embodiment preferably contains epoxy resin (A) from 2% by mass to 30% by mass, more preferably from 3% by mass to 25% by mass. It can be contained in an amount of 5% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 20% by mass or less.

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

(Active ester curing agent)
As the active ester curing agent, the same active ester compound as described in the embodiment of the first invention can be used, and it can be produced in the same manner.
When the active ester curing agent is a resin having a structure represented by the above general formula (1), "B" in the above general formula (1) is represented by the above formulas (B-1) to (B-6). It is preferable that the structure is The structures represented by formulas (B-1) to (B-6) above are all structures with high orientation, so when an active ester curing agent containing them is used, the resulting thermosetting property The cured product of the resin composition has a low dielectric loss tangent and 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 curing agent is calculated based on the total number of aryl carbonyloxy groups and phenolic hydroxyl groups in the resin structure, which provides a cured product with excellent curability and a low dielectric loss tangent. Therefore, it is preferably in the range of 200 g/eq or more and 230 g/eq or less, and more preferably in the range of 210 g/eq or more and 220 g/eq or less.

In the thermosetting resin composition of this embodiment, the blending amount of the active ester curing agent and the epoxy resin is determined so that a cured product with excellent curability and low dielectric loss tangent can be obtained. The ratio of epoxy groups in the epoxy resin is preferably 0.8 to 1.2 equivalents per 1 equivalent of active groups in total. Here, the active group in the active ester curing agent refers to the arylcarbonyloxy group and phenolic hydroxyl group contained in the resin structure.

In the composition of the present 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 based on the entire thermosetting resin composition. % or less, more preferably 1.0% by mass or more and 7% by mass or less.
By containing the specific active ester curing agent in the above range, the resulting cured product can have better dielectric properties and is further excellent in low dielectric loss tangent.

By using an active ester curing agent in combination with a high dielectric constant filler described below, the resin composition of this embodiment has excellent high dielectric constant and low dielectric loss tangent, and has excellent effects even in high frequency bands. .
From the viewpoint of the above effects, the active ester 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, based on 100 parts by mass of the high dielectric constant filler described below. More preferably, it can be contained in an amount of 3 parts by mass or more and 15 parts by mass or less.

Incidentally, as described in JP-A No. 2020-90615, the present applicant has developed a resin composition containing an epoxy resin and a predetermined active ester curing agent in a semiconductor encapsulation application different from the present invention. We are developing. The present invention differs from the technique described in the publication in that it contains a high dielectric constant filler. In addition, since it contains a high dielectric constant filler, the action and effect of the combination of active ester curing agent and epoxy resin are different in that it has a high dielectric constant and also has excellent high dielectric constant and low dielectric loss tangent in high frequency bands. are doing.

(phenolic curing agent)
Examples of phenolic curing agents include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane. Resin, naphthol novolac resin, naphthol-phenol cocondensed novolac resin, naphthol-cresol cocondensed novolac resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked with bismethylene groups), biphenyl-modified naphthol resin (with bismethylene groups) Polyhydric phenol compounds such as polyhydric naphthol compounds with linked phenol nuclei) and aminotriazine-modified phenol resins (polyhydric phenol compounds with phenol nuclei linked with melamine, benzoguanamine, etc.) can be mentioned.

The blending amount of the phenolic curing agent is preferably 20% by mass or more and 70% by mass or less based on the epoxy resin (A). By using the curing agent in an amount within the above range, a resin composition having excellent curability can be obtained.

The content ratio of the phenolic curing agent b to the active ester 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, and Preferably, it can be set to 1.5 or more and 3 or less.
By containing the active ester curing agent and the phenolic curing agent in the above ratio, the resulting cured product can have better dielectric properties and is further excellent in low dielectric loss tangent.

In the composition of the present embodiment, the curing agent (B) containing an active ester curing agent and a phenol curing agent is preferably 0.2% by mass or more and 15% by mass or less based on the entire thermosetting resin composition. , more preferably 0.5% by mass or more and 10% by mass or less, still more preferably 1.0% by mass or more and 7% by mass or less.
By containing the specific active ester curing agent in the above range, the resulting cured product can have better dielectric properties and is further excellent in low dielectric loss 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, titanate Examples include zinc, barium zirconate, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate, and at least one selected from these may be included. By including these high dielectric constant fillers, a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent can be obtained.
From the viewpoint of the effects 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 preferably selected from calcium titanate and magnesium titanate. It is more preferable that at least one of the above is used.

The shape of the high dielectric constant filler is granular, amorphous, flake, etc., and high dielectric constant fillers having 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 even more preferably 0.1 μm or more and 50 μm or less, more preferably 0.3 μm or more and 20 μm or less, and even more preferably .5 μm or more and 10 μm or less.

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, and more preferably 45% by mass or more in 100% by mass of the thermosetting resin composition. The upper limit is about 80% by mass or more.
When the amount of the high dielectric constant filler added is within the above range, the dielectric constant of the obtained cured product will be lower, and the production of molded products will also be excellent.

[Curing catalyst (D)]
The thermosetting resin composition of this embodiment can further contain a curing catalyst (D).
The curing catalyst (D) is sometimes called a curing accelerator. The curing catalyst (D) is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and any known curing catalyst can be used.

As the curing catalyst (D), specifically, a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound; Imidazoles (imidazole curing accelerators) such as 2-methylimidazole and 2-phenylimidazole; amidines and tertiary amines such as 1,8-diazabicyclo[5.4.0]undecene-7 and benzyldimethylamine; , nitrogen atom-containing compounds such as amidine and quaternary salts of amines, and the like, and only one type 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 compounds containing phosphorus atoms, such as tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphine compounds and quinone compounds. It is more preferable to include compounds with latent properties such as adducts between phosphonium compounds and silane compounds, tetra-substituted phosphonium compounds, adducts between phosphine compounds and quinone compounds, and adducts between phosphonium compounds and silane compounds. Adducts are particularly preferred.

By using a combination of an epoxy resin (A) containing a naphthol aralkyl type epoxy resin and a curing catalyst having latent properties, it is possible to obtain a magnetic material with excellent moldability and mechanical strength such as bending strength.

Examples of the organic phosphine include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.
Examples of the tetra-substituted phosphonium compound 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 an anion of an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in its aromatic ring.

AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in an aromatic ring.
x and y are 1 to 3, z is 0 to 3, and x=y.

The compound represented by general formula (6) can be 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 an aromatic organic acid anion is generated in the solution system. Then, by adding water, 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. The above-mentioned phenols include monocyclic phenols such as phenol, cresol, resorcinol, and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol; and bisphenols such as bisphenol A, bisphenol F, and bisphenol S; Examples include polycyclic phenols such as phenylphenol and biphenol.

Examples of the phosphobetaine compound include a compound 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 0-5 and g is 0-3.

The compound represented by general formula (7) can be obtained, for example, as follows.
First, a triaromatic substituted phosphine, which is a tertiary phosphine, is brought into contact with a diazonium salt, and the diazonium group of the triaromatic substituted phosphine and the diazonium salt is substituted.

Examples of the adduct of a phosphine compound and a quinone compound include a compound 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 are bonded to form a cyclic structure. It's okay.

Examples of phosphine compounds used in the adduct of a phosphine compound and a quinone compound include triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trinaphthylphosphine, tris(benzyl)phosphine, etc. It is preferable that the substituent is substituted or has a substituent such as an alkyl group or an alkoxyl group, and examples of the substituent such as an alkyl group or an alkoxyl group include those having 1 to 6 carbon atoms. Triphenylphosphine is preferred from the viewpoint of availability.

Furthermore, examples of the quinone compound used in the adduct of a phosphine compound and a quinone compound include benzoquinone and anthraquinones, and among them, p-benzoquinone is preferred 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 the organic tertiary phosphine and the benzoquinone in a solvent that can dissolve them. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, it is not limited to this.

In the compound represented by 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, A compound to which 4-benzoquinone and triphenylphosphine are added is preferred in that it lowers the thermal modulus of the cured product of the sealing resin composition.

Examples of the adduct of a phosphonium compound and a silane compound include a compound 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 having an aromatic ring or a heterocycle, or an aliphatic group, 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 a group formed by a proton-donating group releasing a proton, and the groups Y ² and Y ³ in the same molecule bond to a silicon atom to form a chelate structure.

Y ⁴ and Y ⁵ represent a group formed by a proton-donating group releasing a proton, and the groups Y ⁴ and Y ⁵ in the same molecule bond to 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 or different from each other.
Z1 is an organic group having an aromatic ring or a heterocycle, or an aliphatic group.

In general formula (9), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group. , ethyl group, n-butyl group, n-octyl group, cyclohexyl group, etc. Among these, alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, and alkoxy groups , an aromatic group having a substituent such as a hydroxyl group, 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 . Similarly, R ²¹ is an organic group that is bonded to groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by a proton-donating group releasing protons, and the groups Y ² and Y ³ in the same molecule bond to a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by a proton-donating group releasing protons, and the groups Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same or different from each other, and the groups Y ² , Y ³ , Y ⁴ and Y5 may be the same or different from each other. The groups represented by -Y ² -R ²⁰ -Y ³ - and Y ⁴ -R ²¹ -Y ⁵ - in general formula (9) are groups in which the proton donor releases two protons. As a proton donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and furthermore, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule constituting the aromatic ring is preferable. An aromatic compound having at least two hydroxyl groups is preferred, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting an aromatic ring is more preferred, such as catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy Naphthalene, 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 Examples include alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin, but among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferred.

^Z1 in the general formula (9) represents an organic group or aliphatic group having an aromatic ring or a heterocycle, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. and aliphatic hydrocarbon groups such as octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl, and biphenyl groups, glycidyloxy groups such as glycidyloxypropyl, mercaptopropyl, and aminopropyl groups, and mercapto Among these, methyl, ethyl, phenyl, naphthyl, and biphenyl groups are more preferable in terms of thermal stability. preferable.
A method for producing an adduct of a phosphonium compound and a silane compound is, for example, as follows.

A silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added and dissolved in a flask containing methanol, and then a sodium methoxide-methanol solution is added dropwise while stirring at room temperature. Furthermore, when a solution prepared in advance in which a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide is dissolved in methanol is added dropwise thereto under 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 the 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 the value within such a numerical range, a sufficient curing accelerating effect can be obtained without excessively deteriorating other properties.

[Inorganic filler]
The thermosetting resin composition of the present embodiment may further contain an inorganic filler in addition to the high dielectric constant filler (C) in order to reduce hygroscopicity, reduce linear expansion coefficient, improve thermal conductivity, and improve strength. I can do it.

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 made of spherical powders, and glass fibers. These inorganic fillers may be used alone or in combination of two or more. Among the above inorganic fillers, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity, and the shape of the filler is spherical from the viewpoint of fluidity during molding and mold abrasion resistance. is preferred.

The blending amount of the inorganic filler other than the high dielectric constant filler (C) is preferably 10% by mass based on 100% by mass of the thermosetting resin composition from the viewpoint of moldability, reduction of thermal expansion, and improvement of strength. The content may be in the range of 15% by mass or more and 40% by mass or less, more preferably 20% by mass or more and 35% by mass or less. Within the above range, thermal expansion property reduction and moldability are excellent.

[Other ingredients]
In addition to the above-mentioned components, the thermosetting resin composition of the present embodiment may contain various components such as a silane coupling agent, a mold release agent, a coloring agent, a dispersant, and a stress reducing agent, as necessary. can.

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 contained in 30% by mass or more in 100% by mass of the composition.
Epoxy resin (A): Contains a biphenylaralkyl epoxy resin and/or a biphenyl epoxy resin.
Curing agent (B): Contains an active ester curing agent and a phenol curing agent.
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, titanium It contains at least one selected from calcium acid zirconate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate.
According to the thermosetting resin composition of the present embodiment which is formed by combining such components, a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent can be obtained, and furthermore, a microstrip equipped with the dielectric substrate can be obtained. Antenna can be provided.

The thermosetting resin composition of this embodiment is
The epoxy resin (A) is preferably contained in 100% by 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, and even more preferably 5% by mass or more and 20% by mass or less. can contain in the amount of
The curing agent (B) is 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, and even more preferably 1.0% by mass. % or more and 7% by mass or less,
The high dielectric constant filler (C) can be contained in 100% by mass of the composition at least 30% by mass, preferably at least 35% by mass, and more preferably at least 45% by mass. The upper limit is 80% by mass.

In this embodiment, the composition includes a combination of an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C), and the high dielectric constant filler (C) is By containing 30% by mass or more in %, it is possible to provide a thermosetting resin composition that provides an excellent dielectric substrate with a high dielectric constant and a low dielectric loss tangent.

The thermosetting resin composition of this embodiment can be manufactured by uniformly mixing the above-mentioned components. Examples of the manufacturing method include a method in which a predetermined amount of raw materials is sufficiently mixed using a mixer, etc., then melt-kneaded using a mixing roll, kneader, extruder, etc., and then cooled and pulverized. The obtained thermosetting resin composition may be made into tablets with a size and mass suitable for molding conditions, if necessary.

The thermosetting resin composition of this embodiment has a spiral 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.

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

The gel time of the thermosetting resin composition of this embodiment is preferably 32 seconds or more and 80 seconds or less, more preferably 35 seconds or more and 70 seconds or less.
By setting the gel time of the thermosetting resin composition to the above-mentioned lower limit or more, the filling property is excellent, and by setting the gel time to the above-mentioned upper limit or less, the moldability becomes good.

Further, the thermosetting resin composition of the present embodiment has a rectangular pressure of 0.1 MPa or more, preferably 0.15 MPa or more, and more preferably 0.20 MPa or more, as measured under the following conditions.
The rectangular pressure is a parameter of melt viscosity, and the smaller the value, the lower the melt viscosity. Since the thermosetting resin composition of this embodiment has a rectangular pressure within the above range, it has excellent mold filling properties during molding.

(conditions)
Using a low-pressure transfer molding machine, the thermosetting resin composition was injected into a rectangular channel with ^a width of 13 mm, a thickness of 1 mm, and a length of 175 mm under conditions of a mold temperature of 175° C. and an injection speed of 177 mm 3 /sec. Then, a pressure sensor buried at a position 25 mm from the upstream end of the flow path measures the change in pressure over time, calculates the minimum pressure when the thermosetting resin composition is flowing, and calculates this minimum pressure as the rectangular pressure. shall be.

The thermosetting resin composition of this embodiment has the following dielectric constant and dielectric loss tangent (tan δ) in a cured product cured by heating at 200° C. for 90 minutes.
The dielectric constant at 25 GHz measured by the cavity resonator method can be 10 or more, preferably 12 or more, and more preferably 13 or more.
The dielectric loss tangent (tan δ) at 25 GHz measured by the cavity resonator method can be 0.04 or less, preferably 0.03 or less, more preferably 0.02 or less, particularly preferably 0.015 or less.

Since the cured product obtained from the thermosetting resin composition of this embodiment has excellent high dielectric constant and low dielectric loss tangent in high frequency bands, it is possible to achieve high frequencies and shorten circuits and miniaturize communication equipment, etc. It can be suitably used as a material for forming a microstrip antenna, a material for forming a dielectric waveguide, a material for forming an electromagnetic wave absorber, etc.

<Microstrip antenna>
The microstrip antenna of this embodiment has the structure shown in FIGS. 1, 2(a) and 2(b) similarly to the embodiment of the first invention, and thus the description thereof will be omitted.

<Dielectric waveguide>
In this embodiment, the dielectric waveguide includes a dielectric formed by curing the thermosetting resin composition of this embodiment, and a conductive 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 metal such as copper, oxide high temperature superconductor, or the like.

<Electromagnetic wave absorber>
In this embodiment, the electromagnetic wave absorber has a structure in which a support, a resistive film, a dielectric layer, and a reflective layer are laminated. The electromagnetic wave absorber can be used as a λ/4 type radio wave absorber having high radio wave absorption performance.
Examples of the support include resin base materials. The support can protect the resistive film and improve its durability as a radio wave absorber.
Examples of the resistive film include indium tin oxide and molybdenum-containing resistive films.
The dielectric layer is formed by curing the thermosetting resin composition of this embodiment. Its thickness is about 10 μm or more and 2000 μm or less.
The reflective layer can function as a radio wave reflective layer, and includes, for example, a metal film.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted within a range that does not impair the effects of the present invention.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.
An example of the first invention (claims 1 to 13 and 22 to 24 as filed) and the first embodiment is shown in Example A.
Example B shows an example of the second invention (Claims 14 to 21 and 22 to 24 as filed) and the second embodiment.

<Example A>
[Examples A1 to A4, Comparative Example A1]
<Preparation of thermosetting resin composition>
The following raw materials were mixed in the contents shown in Table 1 using a mixer at room temperature, and then kneaded with rolls at 70 to 100°C. Next, the obtained kneaded material was cooled and then ground to obtain a powdery thermosetting resin composition. Then, a tablet-shaped thermosetting resin composition was obtained by compression molding under high pressure.

Information on the raw materials in Table 1 is shown below.
(High dielectric constant filler)
・High dielectric constant filler 1: Calcium titanate (CT, average particle size 2.0 μm, manufactured by Fuji Titanium Co., Ltd., relative permittivity at 25°C, 1 GHz: 135)

(Inorganic filler)
・Inorganic filler 1: Alumina (K75-1V25F, manufactured by Denka Corporation)
・Inorganic filler 2: Fused spherical silica (SC-2500-SQ, manufactured by Admatex)

(thermosetting resin)
・Epoxy resin 1: Biphenyl type epoxy resin (YX4000K, manufactured by Mitsubishi Chemical Corporation)
・Epoxy resin 2: Biphenylene skeleton-containing phenol aralkyl epoxy resin (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 In a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer, add 279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride ( The number of moles of acid chloride groups: 2.0 moles) and 1338 g of toluene were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (mol number of phenolic hydroxyl group: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Ta. Thereafter, while performing a nitrogen gas purge, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over a period of 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Furthermore, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration using a decanter to obtain an active ester resin in the form of a toluene solution with a nonvolatile content of 65%. When the structure of the obtained active ester resin was confirmed, it had a structure in which R ¹ and R ³ are hydrogen atoms, Z is a naphthyl group, and l is 0 in the above formula (1-1). Furthermore, the average value k of the repeating units 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 Into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, add 203.0 g of 1,3-benzenedicarboxylic acid dichloride (acid chloride). The number of moles of the group: 2.0 moles) and 1338 g of toluene were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (mol number of phenolic hydroxyl group: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Ta. Thereafter, while performing a nitrogen gas purge, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over a period of 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Furthermore, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration using a decanter to obtain an active ester resin in the form of a toluene solution with a nonvolatile content of 65%. When the structure of the obtained active ester resin was confirmed, it had a structure in which R ¹ and R ³ are hydrogen atoms, Z is a naphthyl group, and l is 0 in the above formula (1-3). The average value k of the repeating units of the active 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 specifically had a structure represented by the following chemical formula. In the following formula, the average value k of the repeating units was 0.5 to 1.0.

(hardening agent)
・Phenol curing agent 1: Biphenylaralkyl type resin (HE910-20, manufactured by Air Water)
・Phenol 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, manufactured by Toray Dow Corning)
・Silane coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sila Ace, manufactured by JNC)

(curing catalyst)
・Curing catalyst 1: Tetraphenylphosphonium-4,4'-sulfonyldiphenolate ・Curing catalyst 2: Tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate

(Release agent)
・Release agent 1: Glycerin trimontanate (Recolb WE-4, manufactured by Clariant Japan)

(Evaluation of permittivity and dielectric loss tangent by cavity resonator method)
The obtained thermosetting resin composition 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 in an oven at 200° C. for 90 minutes under a nitrogen atmosphere, and treated with hydrofluoric acid (immersed in a 2% by mass hydrofluoric acid aqueous solution). After removing the substrate from the hydrofluoric acid, the cured film was peeled off from the Si substrate and used as a test piece.
The measurement devices used were 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 resonant frequency, 3 dB bandwidth, transmitted power ratio, etc. were measured at a frequency of 18 GHz with and without the test piece inserted into the resonator. Then, by analytically calculating these measurement results using software, dielectric properties such as permittivity (Dk) and dielectric loss tangent (Df) were determined. Note that the measurement mode was 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, a thermosetting resin composition for sealing was injected using a low-pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds. It was molded to obtain a test piece of 10 mm x 4 mm x 4 mm. Next, the obtained test piece was post-cured at 175°C for 4 hours, and then measured using a thermomechanical analyzer (TMA100, manufactured by Seiko Electronics Co., Ltd.) at a temperature range of 0°C to 320°C and a heating rate. The measurement was performed under the condition of 5° C./min. From this measurement result, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) were calculated.

(Evaluation of mechanical strength (bending strength, bending modulus))
The obtained thermosetting resin composition was molded using a low-pressure transfer molding machine (KTS-30 manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 130°C, an injection pressure of 9.8 MPa, and a curing time of 300 seconds. Injection molded into a mold. As a result, a molded 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 mechanical strength evaluation was prepared. 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 in accordance with JIS K 6911. .

(Durability under heat)
The cured product of the obtained thermosetting resin composition was subjected to a thermal history of 100 hours at 175° C. 10 times, and then the rate of change in physical properties was evaluated. When the flexural modulus at 260°C before thermal history before repetition is FMa, and the flexural modulus at 260°C before thermal history after repetition is FMb, the rate of change calculated from (FMa-FMb)/FMa x 100% is 200%. If it was within 200%, it was rated as ×, and if it was over 200%, it was rated as ×.

The thermosetting resin compositions of Examples A1 to A4 according to the first invention are excellent in high dielectric constant and low dielectric loss tangent in a high frequency band, and are members ( The results showed that it was possible to form a cured product.
Such a thermosetting resin composition can be suitably used to form a part of a high frequency device such as a microstrip antenna, a dielectric waveguide, and a multilayer antenna.

<Example B>
[Examples B1 to B10, Comparative Example B1]
The following raw materials were mixed in the amounts shown in Table 2 using a mixer at room temperature, and then kneaded with rolls at 70 to 100°C. Next, the obtained kneaded product was cooled and then ground to obtain a powdery resin composition. Then, a tablet-shaped resin composition was obtained by compression molding under high pressure.

(High dielectric constant filler)
・High dielectric constant filler 1: Calcium titanate (average particle size 2.0 μm))

(Inorganic filler)
・Inorganic filler 1: Alumina (DAB25MA-TS3, manufactured by Denka Corporation)
・Inorganic filler 2: Fused spherical silica (SC-2500-SQ, manufactured by Admatex)

(colorant)
・Coloring agent 1: Black titanium oxide (manufactured by Ako Kasei Co., Ltd.)

(coupling agent)
・Coupling agent 1: Phenylaminopropyltrimethoxysilane (CF-4083, manufactured by Dow Corning Toray)
・Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sila Ace, manufactured by JNC)

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

(hardening agent)
・Curing agent 1: Active ester curing agent prepared by the following preparation method (preparation method of active ester curing agent)
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionator tube, and stirrer, add 279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride (number of moles of acid chloride group: 2.0 moles) and 1338 g of toluene. The system was replaced with nitrogen under reduced pressure to dissolve it. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (mol number of phenolic hydroxyl group: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Ta. Thereafter, while performing a nitrogen gas purge, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration using a decanter to obtain an active ester resin in the form of a toluene solution with a nonvolatile content of 65%. When the structure of the obtained active ester resin was confirmed, it had a structure in which R ¹ and R ³ are hydrogen atoms, Z is a naphthyl group, and l is 0 in the above formula (1-1). Furthermore, the average value k of the repeating units was calculated from the reaction equivalence ratio and was in the range of 0.5 to 1.0.
・Curing agent 2: Biphenylene skeleton-containing phenol aralkyl resin (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 phenol resin (Sumilite Resin PR-51470, manufactured by Sumitomo Bakelite Co., Ltd.)
・Curing agent 5: Zylock type phenol aralkyl type phenol curing agent (MEHC-7800SS, manufactured by Meiwa Kasei Co., Ltd.)
・Curing agent 6: Polyvalent MAR type phenol curing agent (SH-002-02, manufactured by Meiwa Kasei Co., Ltd.)
・Curing agent 7: Active ester curing agent prepared by the following preparation method (method for preparing active ester curing agent)
203.0 g of 1,3-benzenedicarboxylic acid dichloride (number of moles of acid chloride group: 2.0 moles) and 1338 g of toluene were placed in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. After charging, the system was replaced with nitrogen under reduced pressure to dissolve. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g (mol number of phenolic hydroxyl group: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Ta. Thereafter, while performing a nitrogen gas purge, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over a period of 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Furthermore, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration using a decanter to obtain an active ester resin in the form of a toluene solution with a nonvolatile content of 65%. When the structure of the obtained active ester resin was confirmed, it had a structure in which R ¹ and R ³ are hydrogen atoms, Z is a naphthyl group, and l is 0 in the above formula (1-3). The average value k of the repeating units of the active 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 specifically had a structure represented by the following chemical formula. In the following formula, the average value k of the repeating units was 0.5 to 1.0.

(catalyst)
・Catalyst 1: Tetraphenylphosphonium-4,4'-sulfonyl diphenolate

(Evaluation of permittivity and dielectric loss tangent by cavity resonator method)
First, a test piece was obtained using a resin composition.
Specifically, the resin compositions prepared in Examples and Comparative Examples were applied to a Si substrate and prebaked at 120° C. for 4 minutes to form a resin film with a coating thickness of 12 μm.
This was heated in an oven at 200° C. for 90 minutes under a nitrogen atmosphere, and treated with hydrofluoric acid (immersed in a 2% by mass hydrofluoric acid aqueous solution). After removing the substrate from the hydrofluoric acid, the cured film was peeled off from the Si substrate and used as a test piece.
The measurement devices used were 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 resonant frequency, 3 dB bandwidth, transmitted power ratio, etc. were measured at a frequency of 25 GHz with and without the test piece inserted into the resonator. Then, by analytically calculating these measurement results using software, dielectric properties such as permittivity (Dk) and dielectric loss tangent (Df) were determined. Note that the measurement mode was TE ₀₁₁ mode.

(Spiral flow measurement)
Using a low-pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement according to EMMI-1-66 was molded at a mold temperature of 175°C, an injection pressure of 6.9 MPa, and curing. The resin compositions obtained in Examples and Comparative Examples were injected for a time of 120 seconds, 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., and the time (unit: seconds) until hardening was measured while kneading with a spatula.

(molding shrinkage rate)
For each Example and Comparative Example, the molding shrinkage rate (after ASM) of the obtained resin composition was measured after molding (as Mold), and after the molding, it was fully cured and used as a dielectric substrate. The molding shrinkage rate (after PMC) was evaluated under heating conditions (PMC: Post Mold Cure) assumed to be produced.
First, a JIS The molding shrinkage rate (after ASM) was obtained according to K 6911.
Further, the obtained test piece was heat treated at 175° C. for 4 hours, and the molding shrinkage rate (after ASM) was measured according to 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 obtained cured resin composition were measured as follows. First, a sealing resin composition was injection molded using a low pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds. A test piece of 10 mm x 4 mm x 4 mm was obtained. Next, the obtained test piece was post-cured at 175°C for 4 hours, and then measured using a thermomechanical analyzer (TMA100, manufactured by Seiko Electronics Co., Ltd.) at a temperature range of 0°C to 320°C and a heating rate. The measurement was performed under the condition of 5° C./min. From this measurement result, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) were calculated.

(Evaluation of mechanical strength (bending strength/flexural modulus))
The resin compositions of Examples and Comparative Examples were molded using a low-pressure transfer molding machine (KTS-30 manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 130°C, an injection pressure of 9.8 MPa, and a curing time of 300 seconds. Injection molded into a mold. As a result, a molded 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 mechanical strength evaluation was prepared. 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 in accordance with JIS K 6911. .

From the results in Table 2, it can be seen that according to the thermosetting resin composition of the second invention, a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent, or in other words, excellent in balance of these properties, can be obtained. It became clear. Furthermore, it has been revealed that the thermosetting resin composition of the present invention has a long spiral flow flow length and a gel time within an appropriate range, and therefore has excellent moldability.

This application is filed in Japanese Patent Application No. 2021-051748 filed on March 25, 2021, Japanese Patent Application No. 2021-172197 filed on October 21, 2021, and filed on December 6, 2021. Japanese Patent Application No. 2021-197667 filed on December 6, 2021, Japanese Patent Application No. 2021-197679 filed on December 6, 2021, 2021 Claims priority based on Japanese Patent Application No. 2021-197720 filed on December 6, 2021 and Japanese Patent Application No. 2021-197731 filed on December 6, 2021, and all of the disclosures thereof Import here.

10 Microstrip antenna 12 Dielectric substrate 14 Radiation conductor plate 16 Ground conductor plate 20, 20' Microstrip antenna 22 Dielectric substrate 24 High dielectric substrate 26 Spacer a Cavity part

Claims (24)

thermosetting resin;
A high dielectric constant filler with a relative dielectric constant of 10 or more at 25° C. and 25 GHz,
an active ester compound;
A thermosetting resin composition comprising,
When the flexural modulus at 25°C is FM ₂₅ and the flexural modulus at 260°C is FM ₂₆₀ , measured according to the following procedure, FM ₂₅ and FM ₂₆₀ are 0.005≦FM ₂₆₀ /FM ₂₅ ≦0 .1 is satisfied.
Thermosetting resin composition.
(procedure)
The thermosetting resin composition was injection-molded into a mold using a low-pressure transfer molding machine under the conditions of a mold temperature of 130°C, an injection pressure of 9.8 MPa, and a curing time of 300 seconds. A molded product with a length of 80 mm is obtained.
The obtained molded product is post-cured at 175° C. for 4 hours to prepare a test piece.
The flexural modulus (N/mm ² ) of the test piece at room temperature (25° C.) or 260° C. is measured in accordance with JIS K 6911. When the bending strength at 25°C is FS ₂₅ and the bending strength at 260°C is FS ₂₆₀ , which is measured according to JIS K 6911 according to the above procedure, FS ₂₅ and FS ₂₆₀ are 0.025≦FS ₂₆₀ / The thermosetting resin composition according to claim 1, which satisfies _FS25 ≦0.2. The thermosetting resin composition according to claim 1 or 2, wherein the cured product of the thermosetting resin composition has a glass transition temperature of 100°C or more and 250°C or less. 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 above the glass transition temperature and 320° C or less is 30 ppm. The thermosetting resin composition according to any one of claims 1 to 3, which has a content of 100 ppm/°C or more and 100 ppm/°C or less. The thermosetting resin composition according to any one of claims 1 to 4, wherein the high dielectric constant filler contains calcium titanate. Thermosetting according to any one of claims 1 to 5, wherein 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. Resin composition. The active ester compound is selected from an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. The thermosetting resin composition according to any one of claims 1 to 6, comprising at least one of: The thermosetting resin composition according to any one of claims 1 to 7, wherein 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 via an aliphatic cyclic hydrocarbon group,
Ar' is a substituted or unsubstituted aryl group,
B is a structure represented by the following general formula (B),

(In the general formula (B), Ar is a substituted or unsubstituted arylene group, and Y is a single bond, a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted is a cyclic alkylene group having 3 to 6 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group. n is 0 It is an integer between ~4.)
k is the average value of repeating units and ranges from 0.25 to 3.5. ) The thermosetting resin composition according to any one of claims 1 to 8, wherein the thermosetting resin contains an epoxy resin containing a biphenylene skeleton. The thermosetting resin composition according to any one of claims 1 to 9, further comprising a phenolic curing agent. The thermosetting resin composition according to claim 10, wherein the phenolic curing agent contains a phenolic resin containing a biphenylene skeleton. The thermosetting resin composition according to any one of claims 1 to 11, which is used to form a part of a high frequency device selected from the group consisting of a microstrip antenna, a dielectric waveguide, and a multilayer antenna. . A high frequency device comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 12. (A) an epoxy resin;
(B) a curing agent;
(C) a high dielectric constant filler;
A thermosetting resin composition comprising,
The epoxy resin (A) contains a biphenylaralkyl-type epoxy resin and/or a biphenyl-type epoxy resin (excluding a biphenylaralkyl-type epoxy resin),
The curing agent (B) contains an active ester curing agent and a phenolic 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, Containing at least one selected from calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate,
A thermosetting resin composition containing a high dielectric constant filler (C) in an amount of 30% by mass or more in 100% by mass of the thermosetting resin composition. The thermosetting resin composition according to claim 14, wherein the high dielectric constant filler (C) is at least one selected from calcium titanate, strontium titanate, and magnesium titanate. The active ester curing agent includes an active ester curing agent containing a dicyclopentadiene diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolak, and a phenol novolak. The thermosetting resin composition according to claim 14 or 15, wherein the thermosetting resin composition is at least one selected from active ester curing agents including benzoylated products. The thermosetting resin composition according to any one of claims 14 to 16, wherein the active ester curing agent has a structure represented by the following general formula (1).

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

(In the general formula (B), Ar is a substituted or unsubstituted arylene group, and Y is a single bond, a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted is a cyclic alkylene group having 3 to 6 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group. n is 0 It is an integer between ~4.)
k is the average value of repeating units and ranges from 0.25 to 3.5. ) The thermosetting resin composition according to any one of claims 14 to 17, further comprising a curing catalyst (D). The thermosetting resin composition according to any one of claims 14 to 18, which is used as a material for forming a microstrip antenna. The thermosetting resin composition according to any one of claims 14 to 18, which is used as a material for forming a dielectric waveguide. The thermosetting resin composition according to any one of claims 14 to 18, which is 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 surface of the dielectric substrate;
a ground conductor plate provided on the other surface of the dielectric substrate;
Microstrip antenna. A dielectric substrate,
a radiation conductor plate provided on one surface of the dielectric substrate;
a ground conductor plate provided on the other surface of the dielectric substrate;
a high dielectric material disposed opposite to the radiation conductor plate;
A microstrip antenna comprising:
A microstrip antenna, wherein the high dielectric material is constituted by the dielectric substrate according to claim 22.

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