TW202248273A - Thermosetting resin composition, high frequency device, dielectric substrate, and microstrip antenna - Google Patents

Abstract

A thermosetting resin composition according to the present invention comprises: a thermosetting resin, a high dielectric constant filler having a specific dielectric constant at 25 DEG C and 25 GHz of 10 or higher; and an active ester compound, and when the flexural modulus of elasticity at 25 DEG C is denoted by FM25, and the flexural modulus of elasticity at 260 DEG C is denoted by FM260, FM25 and FM260 satisfy 0.005 ≤ FM260/FM25 ≤ 0.1. Moreover, the thermosetting resin composition according to the present invention comprises an epoxy resin (A), a curing agent (B), and a high dielectric constant filler (C). The epoxy resin (A) includes a biphenyl aralkyl-type epoxy resin and/or a biphenyl-type epoxy resin (excluding biphenyl aralkyl-type epoxy resins). The curing agent (B) includes an active ester-based curing agent and a phenol-based curing agent. The high dielectric constant filler (C) includes at least one type selected from calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium zirconate-titanate, lead zirconate-titanate, barium magnesium niobate, and calcium zirconate, and the high dielectric constant filler (C) is contained at an amount of 30 mass% or higher in 100 mass% of the thermosetting resin composition.

Description

Thermosetting resin composition, high-frequency device, dielectric substrate, and microstrip antenna

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

In recent years, the speed of wireless communication has increased, and the performance and miniaturization of the communication equipment used have been demanded. Furthermore, in recent years, the capacity of wireless communication has increased rapidly, and the use frequency of transmission signals has been rapidly increased in broadband and high frequency along with this. Therefore, the frequency band used by communication equipment cannot be dealt with only by the microwave frequency band used in the past, and is expanding to the millimeter wave frequency band. Against such a background, there is a strong demand for higher performance of antennas mounted on communication equipment.

In communication equipment, if the dielectric constant of the antenna material (dielectric substrate) incorporated inside the communication equipment is increased, further miniaturization can be achieved. In addition, if the dielectric loss tangent of the dielectric substrate is reduced, the loss becomes low, which is advantageous for high frequency. Therefore, if a dielectric substrate with a high dielectric constant and a small dielectric loss tangent can be used, it is possible to increase the frequency, shorten the circuit, and reduce the size of the communication device.

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

Patent Document 2 discloses a resin composition containing a siloxane-modified polyamideimide resin, a high dielectric constant filler, and an epoxy resin. The constant is 15 or more. Examples of using barium titanate as the high dielectric constant filler are described in Examples of this document.

Patent Document 3 discloses a resin composition containing an epoxy resin, a dielectric powder, a nonionic surfactant, and an active ester-based hardener. This document describes that the resin composition can be used as a high-permittivity insulating material for electronic components used in a high-frequency region, and as a high-permittivity insulating material for fingerprint sensors. Examples of using barium titanate as the dielectric powder are described in Examples of this document.

Patent Document 4 discloses a resin composition for molding, which contains an epoxy resin, a curing agent, and an inorganic filler containing calcium titanate particles and strontium titanate particles in a specific amount. At least one of the group consisting of silica particles and alumina particles is used for sealing electronic parts in high-frequency devices. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-41998 [Patent Document 2] Japanese Unexamined Patent Publication No. 2004-315653 [Patent Document 3] Japanese Patent Laid-Open No. 2020-105523 [Patent Document 4] Japanese Patent No. 6870778

[Problem to be Solved by the Invention]

However, in the conventional techniques described in Patent Document 1 to Patent Document 4, there is room for improvement in the following points. It is clear that in the composite material described in Patent Document 1, there is room for improvement in terms of high dielectric constant and low dielectric loss tangent in higher frequency bands, and also in terms of thermal durability. Make it your first topic. Furthermore, the dielectric substrates described in Patent Document 1 to Patent Document 4 have problems in terms of high dielectric constant and low dielectric loss tangent, and this problem is particularly significant in high frequency bands. Make it a second subject. [Technical means to solve the problem]

The inventors of the present invention found that by using a high dielectric constant filler and an active ester compound in a thermosetting resin composition, the ratio of the flexural modulus at 260°C to the flexural modulus at 25°C Controlled within an appropriate range, the above-mentioned first problem can be solved, and the first invention has been completed. That is, the first invention can be shown as follows.

According to the first invention, a thermosetting resin composition is provided, which contains: a thermosetting resin; a high dielectric constant filler having a specific dielectric constant of 10 or more at 25°C and 25 GHz; In the following sequential measurements, when the flexural modulus at 25°C is set to FM ₂₅ and the flexural modulus at 260°C is set to FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ satisfy 0.005≤FM ₂₆₀ /FM ₂₅ ≤0.1. (Procedure) Using a low-pressure transfer molding machine, the thermosetting resin composition was injected into a mold under the conditions of a mold temperature of 130° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds to obtain a mold with a width of 10 mm. A molded product with a thickness of 4 mm and a length of 80 mm. The obtained molded product was post-hardened at 175° C. for 4 hours to produce a test piece. The flexural modulus (N/mm ² ) of the test piece at room temperature (25° C.) or 260° C. was measured in accordance with JIS K 6911.

Also, according to the first invention, there is provided a high-frequency device including a cured product of the above-mentioned thermosetting resin composition.

Moreover, the inventors of the present invention found that the above-mentioned 2nd subject can be solved by the combination of a specific component, and completed 2nd invention. That is, the 2nd invention can be shown as follows. According to the second invention, there is provided a kind of thermosetting resin composition, which contains: (A) epoxy resin; (B) hardeners; and (C) a high dielectric constant filler, and The epoxy resin (A) contains biphenyl aralkyl type epoxy resin and/or biphenyl type epoxy resin (excluding biphenyl aralkyl type epoxy resin), Hardener (B) contains active ester hardener and phenolic hardener, A thermosetting resin composition can be provided, wherein the high dielectric constant filler (C) contains: calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, titanium Bismuth acid, zirconium titanate, zinc titanate, barium zirconate, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate and calcium zirconate, in the aforementioned thermosetting resin composition In 100% by mass, the high dielectric constant filler (C) is contained in an amount of 30% by mass or more.

According to the second invention, there is provided a dielectric substrate obtained by curing the aforementioned thermosetting resin composition.

According to the first or second invention, a microstrip antenna is provided, which has: The aforementioned dielectric substrate; a radiation conductor plate disposed on one side of the aforementioned dielectric substrate; and The ground conductor plate is provided on the other side of the dielectric substrate.

According to the first or second invention, a microstrip antenna is provided, which has: Dielectric substrate; a radiation conductor plate disposed on one side of the aforementioned dielectric substrate; a grounding conductor plate disposed on the other side of the aforementioned dielectric substrate; and a high dielectric body disposed opposite to the aforementioned radiating conductor plate, and The high dielectric body is composed of the dielectric substrate. [Effect of Invention]

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 thermal durability, and a high-frequency device using the thermosetting resin composition. Also, according to the second invention, it is possible to provide a thermosetting resin composition capable of obtaining a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent and excellent in formability, and a dielectric substrate containing the resin composition , and a microstrip antenna provided with the dielectric substrate. In other words, the thermosetting resin composition of the second invention can obtain a dielectric substrate having an excellent balance of high dielectric constant and low dielectric loss tangent.

Hereinafter, based on the first embodiment, the first invention (claims 1-13, 22-24 at the time of application) will be described with reference to the drawings, and the second invention (claim 14 at the time of application) will be described according to the second embodiment with reference to the drawings. ～21, 22～24) for explanation. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. Also, for example, unless otherwise specified, "1 to 10" means "1 or more" to "10 or less".

[First invention] The outline of the thermosetting resin composition of the first embodiment will be described.

The thermosetting resin composition of the present embodiment is composed of: a thermosetting resin; a high dielectric constant filler having a specific permittivity of 10 or more at 25° C. and 25 GHz; and an active ester compound in the following order: As measured, 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 satisfy 0.005≤FM ₂₆₀ /FM ₂₅ ≤0.1.

The lower limit of FM ₂₆₀ /FM ₂₅ is at least 0.005, preferably at least 0.006, more preferably at least 0.007, and still more preferably at least 0.008. Thereby, in a member having a high dielectric constant and a low dielectric loss tangent (a cured product of a thermosetting resin composition), thermal durability can be improved. On the other hand, the upper limit of FM ₂₆₀ /FM ₂₅ can be set to, for example, 0.1 or less, preferably 0.05 or less, more preferably 0.03 or less, and still more preferably 0.02 or less. Thereby, the balance of physical properties in the cured product of the thermosetting resin composition can be achieved.

Today, the temperature of the working environment is increasing due to design situations such as higher frequency, higher output of power semiconductors, and lower height of devices. In order to cope with such an increase in the temperature of the working environment, the inventors studied the thermal characteristics of the cured product of the thermosetting resin composition. According to the knowledge of the present inventors, the index of FM ₂₆₀ /FM ₂₅ can stably evaluate the difficulty of deformation of the cured product of the thermosetting resin composition before and after heat treatment. Also, it is clear that by setting FM ₂₆₀ /FM ₂₅ as an index to be more than the above-mentioned lower limit value, it is possible to suppress the thermal deterioration of the cured product due to heating, and therefore it is possible to improve the thermal durability of the member formed using the cured product. sex. In addition, in the above-mentioned members, it is also expected to suppress a decrease in dielectric properties due to thermal deterioration.

In this embodiment, for example, by appropriately selecting the types and amounts of each component contained in the thermosetting resin composition, the blending amount, the preparation method of the thermosetting resin composition, etc., the above-mentioned FM ₂₆₀ /FM ₂₅ can be controlled. , the following FS ₂₆₀ /FS ₂₅ , glass transition temperature and linear expansion coefficient. Among these, for example, biphenyl type epoxy resins using calcium titanate as a high dielectric constant filler, the content of the high dielectric constant filler, aluminum oxide as an inorganic filler, and a thermosetting resin And/or phenol aralkyl-type epoxy resins containing biphenylene skeletons, active ester compounds containing dicyclopentadiene-type diphenol structures as active ester compounds, and biphenylaralkylenes as phenolic hardeners Base type resin and/or phenol aralkyl type resin containing biphenylene skeleton, etc., as used to set the above FM ₂₆₀ /FM ₂₅ , the following FS ₂₆₀ /FS ₂₅ , glass transition temperature and linear expansion coefficient Elements within the expected numerical range.

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

The lower limit of FS ₂₆₀ /FS ₂₅ is at least 0.025, preferably at least 0.028, more preferably at least 0.030, still more preferably at least 0.032. Thereby, in a member having a high dielectric constant and a low dielectric loss tangent (a cured product of a thermosetting resin composition), thermal toughness can be improved. On the other hand, the upper limit of FS ₂₆₀ /FS ₂₅ may be, for example, 0.2 or less, preferably 0.1 or less, more preferably 0.07 or less, and still more preferably 0.05 or less. Thereby, the balance of physical properties in the cured product of the thermosetting resin composition can be achieved.

(Measurement procedure for flexural elastic modulus and flexural strength) Using a low-pressure transfer molding machine, inject a thermosetting resin composition into a mold under the conditions of a mold temperature of 130°C, an injection pressure of 9.8MPa, and a curing time of 300 seconds. , thereby obtaining a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm. The obtained molded product was post-hardened at 175° C. for 4 hours to produce a test piece. According to JIS K 6911, the flexural elastic 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 crosshead speed of 5 mm/min.

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

The cured product of this thermosetting resin composition has a linear expansion coefficient in the range below the glass transition temperature as CTE1, and a linear expansion coefficient in the range exceeding the glass transition temperature and 320° C. or lower as CTE2. CTE1 is, for example, not less than 5 ppm/°C and not more than 25 ppm/°C, preferably not less than 5 ppm/°C and not more than 23 ppm/°C. CTE2 is, for example, not less than 30 ppm/°C and not more than 100 ppm/°C, preferably not less than 30 ppm/°C and not more than 90 ppm/°C.

Hereinafter, each component of the thermosetting resin composition of this embodiment is described in detail.

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

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

As for the epoxy resin, for example, biphenyl type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin; Stilbene type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin and other novolak type epoxy resins; trisphenol methane type epoxy resin, alkyl modified trisphenol methane type epoxy resin, etc. Polyfunctional epoxy resins such as triphenol-type epoxy resins exemplified in ; phenol aralkyl-type epoxy resins with phenylene skeletons, naphthol aralkyl-type epoxy resins with phenylene skeletons, bifunctional epoxy resins with biphenylene Phenyl aralkyl type epoxy resin with phenylene skeleton, naphthol aralkyl type epoxy resin with biphenylene skeleton, etc. phenol aralkyl type epoxy resin; epoxy resin with biphenylene skeleton ; Dihydroxynaphthalene type epoxy resin, epoxy resin obtained by glycidyl etherification of dimer of dihydroxynaphthalene, such as naphthol type epoxy resin; triglycidyl isocyanate, mono Allyl Diglycidyl Trimeric Isocyanate and other three-nuclear epoxy resins; dicyclopentadiene-modified phenol-type epoxy resins and other cross-linked cyclic hydrocarbon-modified phenol-type epoxy resins, etc. These may be used alone or in combination of two or more.

Among these, it is preferably an epoxy resin containing a biphenylene skeleton, more preferably an epoxy resin containing a biphenyl aralkyl type epoxy resin and a biphenyl type epoxy resin (biphenyl aralkyl type epoxy resin) Except for one or more of the groups formed.

The content of the thermosetting resin is, for example, 2 mass % or more in 100 mass % of the thermosetting resin composition, preferably 5 mass % or more, more preferably 7 mass % or more. Also, 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 in 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). Examples of high dielectric constant fillers include calcium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, zirconate titanate Calcium, lead zirconate titanate, barium magnesium niobate, calcium zirconate, etc., one or two or more selected from these can be used.

Regarding the high dielectric constant filler, in the above example, at least one of calcium titanate and strontium titanate may be contained, preferably calcium titanate is contained. Thereby, the dielectric loss tangent in the high frequency band can be further reduced.

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

The shape of the high dielectric constant filler is granular, amorphous, flaky, etc., and the high dielectric constant filler of these shapes can be used in any proportion.

The content of the high dielectric constant filler is preferably 30 mass % to 90 mass % in 100 mass % of the thermosetting resin composition, more preferably 35 mass % to 80 mass %, further preferably 40 mass % to 70 mass % %In the range. When the added amount of the high dielectric constant filler is within the above range, the obtained cured product has a lower dielectric constant and is also excellent in the manufacture of molded articles.

[Active ester compound] The thermosetting resin composition of this embodiment contains an active ester compound (active ester curing agent). Active ester compounds function as hardeners for thermosetting resins such as epoxy resins.

As an active ester compound, the compound which has one or more active ester groups in 1 molecule can be used. Among them, the active ester compound is preferably one having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. compound.

Preferred specific examples of active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolaks, Active ester compound of benzoyl compounds containing phenol novolac. The active ester compound can contain at least 1 sort(s) selected from these. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit including a phenylene-dicyclopentylene-phenylene group.

In this embodiment, the resin which has the structure represented by the following general formula (1), for example can be used for an active ester compound.

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

In formula (B), Ar is a substituted or unsubstituted arylene group. The substituent of the substituted arylene group includes 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, substituted or unsubstituted straight-chain alkylene with 1 to 6 carbons or substituted or unsubstituted cyclic alkylene with 3 to 6 carbons, substituted or unsubstituted A divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a pyloxy group. Examples of the substituent of the aforementioned 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. As Y, a single bond, a methylene group, -CH(CH ₃ ) ₂ -, an ether bond, an optionally substituted cycloalkylene, and an optionally substituted 9,9-xylene group are preferably mentioned. (9,9-fluoronylene), etc. n is an integer of 0-4, preferably 0 or 1. Specifically, B is a structure represented by the following general formula (B1) or the following general formula (B2).

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

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

By containing the specific active ester compound in the thermosetting resin composition of this embodiment, the obtained cured product can have excellent dielectric properties and excellent 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 hardening reaction of 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 form a secondary hydroxyl group. The secondary hydroxyl group is blocked by the ester residue of the active ester compound. Therefore, the dielectric loss tangent of the cured product can be 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 the formulas (B-1) to (B-6), R ¹ are each independently a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a phenyl group, an aralkyl group any of

R ² are each independently any one of an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, and a phenyl group, and X is a linear chain extension group with 2 to 6 carbons, an ether bond, or a carbonyl group , a carbonyloxy group, a sulfide group, and a pyrenyl group, n is an integer of 0-4, and p is an integer of 1-4.

The structures represented by the above formulas (B-1) to (B-6) are highly oriented structures, so when using an active ester compound containing them, the cured product of the thermosetting resin composition obtained It is possible to have a low dielectric loss tangent in a high frequency band. Among them, from the viewpoint of low dielectric loss tangent, it is preferably an active ester compound having a structure represented by formula (B-2), formula (B-3) or formula (B-5), more preferably further A structure in which n is 0 in formula (B-2), a structure in which X is an ether bond in formula (B-3), or a structure in which two carbonyloxy groups are located at the 4,4'-position in formula (B-5) active ester compounds. Also, it is preferable that all R ¹ in each formula are hydrogen atoms.

"Ar'" in formula (1) is an aryl group, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 3,5-xylyl, o-biphenyl, m-biphenyl , p-biphenyl, 2-benzylphenyl, 4-benzylphenyl, 4-(α-cumyl)phenyl, 1-naphthyl, 2-naphthyl, etc. Among them, 1-naphthyl or 2-naphthyl is preferable from the viewpoint of obtaining a cured product with a low dielectric loss tangent.

In this embodiment, [A] in the active ester compound represented by formula (1) is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group. As such an arylene group, for example, Examples include structures obtained by subjecting an unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule to a complex addition reaction with a phenolic compound.

Regarding the aforementioned unsaturated aliphatic cyclic hydrocarbons containing two double bonds in one molecule, for example, dicyclopentadiene, a polymer of cyclopentadiene, tetrahydroindene, 4-vinyl Cyclohexene, 5-vinyl-2-norcamphene, limonene, and the like may be used alone, or two or more of them may be used in combination. Among these, dicyclopentadiene is preferable from the viewpoint that a cured product excellent in heat resistance can be obtained. In addition, since dicyclopentadiene is contained in petroleum fractions, polymers of cyclopentadiene, other aliphatic or aromatic diene compounds, etc. may be contained as impurities in industrial dicyclopentadiene, However, considering performances such as heat resistance, curability, and formability, it is desirable to use a dicyclopentadiene having a purity of 90% by mass or more.

On the other hand, the aforementioned phenolic compounds include, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropylphenol, Allylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2 ,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. may be used individually or in combination of 2 or more types. Among these, phenol is preferable from the viewpoint of being an active ester compound having high curability and excellent dielectric properties of a cured product.

In a preferred embodiment, [A] in the active ester compound represented by formula (1) has a structure represented by formula (A). The cured product of the thermosetting resin composition containing the active ester compound in which [A] in the formula (1) has the following structure can achieve a low dielectric loss tangent in the high frequency band.

In formula (A), R ³ are each independently a hydrogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a phenyl group, and an aralkyl group, and l is 0 or 1, m is an integer of 1 or more.

As more preferable ones among the active ester compounds represented by formula (1), the resins represented by the following formula (1-1), formula (1-2) and formula (1-3) can be mentioned, as particularly preferred Examples thereof 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 with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a phenyl group, and an aralkyl group, Z is phenyl, naphthyl, or phenyl or naphthyl having 1 to 3 alkyl groups with 1 to 4 carbons on the aromatic nucleus, l is 0 or 1, k is the average of repeating units, and is 0.25 to 3.5.

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

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

The active ester compound represented by the above-mentioned general formula (A) can be produced by the following known method: a phenolic compound having a structure formed by aliphatic cyclic hydrocarbon group and a plurality of aryl groups having phenolic hydroxyl groups (a ), containing aromatic nucleodicarboxylic acid or its halide (b) and aromatic monohydroxy compound (c) for reaction.

The reaction ratio of the above-mentioned phenolic compound (a), aromatic core-containing dicarboxylic acid or its halide (b) and aromatic monohydroxyl compound (c) can be appropriately adjusted according to the desired molecular design, but among them, it is possible to obtain From the viewpoint of an active ester compound with higher hardening properties, it is preferable to use the above-mentioned phenolic compound with respect to a total of 1 mole of carboxyl groups or acid halide groups contained in the aromatic core-containing dicarboxylic acid or its halide (b). The ratio of the phenolic hydroxyl group possessed by the compound (a) within the range of 0.25 to 0.90 moles and the hydroxyl group possessed by the aforementioned aromatic monohydroxy compound (c) within the range of 0.10 to 0.75 moles is more preferably the ratio of each raw material It is used in such a ratio that the phenolic hydroxyl group possessed by the aforementioned phenolic compound (a) is within the range of 0.50 to 0.75 moles and the hydroxyl group possessed by the aforementioned aromatic monohydroxy compound (c) is within the range of 0.25 to 0.50 moles. Each raw material.

Also, when the total number of arylcarbonyloxy groups and phenolic hydroxyl groups in the resin structure is used as the number of functional groups of the resin, it is possible to obtain a cured product with excellent curability and a low dielectric loss tangent. The functional group equivalent weight of the active ester compound is preferably in the range of 200 g/eq to 230 g/eq, more preferably in the range of 210 g/eq to 220 g/eq.

In the thermosetting resin composition of this embodiment, from the viewpoint of obtaining a cured product having excellent curability and a low dielectric loss tangent, the content of the active ester compound and the epoxy resin is preferably at a ratio as follows: The total amount of active groups in the active ester compound is 1 equivalent, and the epoxy groups in the epoxy resin are 0.8 to 1.2 equivalents. Here, the active group in the active ester compound refers to the aryl carbonyloxy group and the phenolic hydroxyl group in the resin structure.

The active ester compound is preferably at least 0.5% by mass and not more than 15% by mass, more preferably at least 2% by mass and not more than 12% by mass, and still more preferably at least 2% by mass in 100% by mass of the thermosetting resin composition. The amount of mass % or less is used. By containing the specific active ester compound within the above range, the obtained cured product can have more excellent dielectric properties, and the low dielectric loss tangent is further excellent.

The thermosetting resin composition of the present embodiment has a high dielectric constant and a low dielectric loss tangent by using the active ester compound in combination with the above-mentioned high dielectric constant filler, and these effects are excellent even in a high frequency band. From the viewpoint of the above effect, the active ester compound can be contained in the following manner: with respect to 100 parts by mass of the above-mentioned high dielectric constant filler, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass parts or less, more preferably 3 parts by mass or more and 15 parts by mass or less.

[hardener] The thermosetting resin composition of this embodiment can contain other hardening|curing agents other than an active ester compound. As other curing agents, phenol-based curing agents, amine compound-based curing agents, amide compound-based curing agents, acid anhydride-based curing agents, and the like can be used. These may be used alone or in combination of two or more. Among them, a phenolic curing agent can be used.

As the phenolic curing agent, for example, phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, biphenylene skeleton-containing phenol Resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylol ethane resins, naphthol novolak resins, naphthol-phenol novolak resins, naphthalene Phenol-cresol co-denatured novolac resin, biphenyl modified phenolic resin (polyphenolic compound formed by linking the phenolic core through double methylene), biphenyl modified naphthol resin (phenolic core through double methylene Polyhydric naphthol compound formed by linking), amino-tri-methanol modified phenolic resin (polyphenolic compound formed by linking phenolic nuclei with melamine, benzoguanamine, etc.) and other polyphenolic compounds. Among them, biphenyl aralkyl type phenol resins can be used.

As for the amine compound-based curing agent, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminediphenylene, isophoronediamine, imidazole, BF ₃ -amine Amine compounds such as complexes and guanidine derivatives. As the amide compound-based curing agent, for example, a polyamide resin synthesized from dicyandiamine, a dimer of linolenic acid, and ethylenediamine is mentioned. As for the acid anhydride hardener, for example, phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, pyromelite dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, Base resistance to acid anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride.

When a curing agent is used, the compounding amount thereof is preferably from 0.5% by mass to 15% by mass, more preferably from 1% by mass to 10% by mass, relative to 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.

[Hardening Catalyst] The thermosetting resin composition may also contain a curing catalyst. The hardening catalyst is sometimes called a hardening accelerator or the like. The curing catalyst is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and known curing catalysts can be used.

Specifically, phosphorus atom-containing compounds such as organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, etc.; - imidazoles (imidazole-based hardening accelerators) such as methylimidazole and 2-phenylimidazole; amidines exemplified by 1,8-diacribicyclo[5.4.0]undecene-7, benzyldimethylamine, etc., or Nitrogen atom-containing compounds such as tertiary amines, amidines, or quaternary salts of amines may be used alone or in combination of two or more.

Among them, from the viewpoint of improving hardenability and obtaining a magnetic material excellent in mechanical strength such as bending strength, it is preferable to contain a phosphorus atom-containing compound, and it is more preferable to contain a tetrasubstituted phosphonium compound, a phosphobetaine compound, or a phosphine compound. Those with latent properties such as adducts of quinone compounds, adducts of phosphonium compounds and silane compounds, especially tetrasubstituted phosphonium compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds .

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

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

When using a hardening catalyst, its content is preferably 0.05-3 mass % in 100 mass % of thermosetting resin compositions, More preferably, it is 0.08-2 mass %. By setting it as such a numerical value range, the hardening acceleration effect can fully be acquired, without deteriorating other performance too much.

[Inorganic filler material] The thermosetting resin composition of the present embodiment may contain inorganic fillers in addition to high dielectric constant fillers to reduce hygroscopicity, reduce linear expansion coefficient, improve thermal conductivity, and increase strength.

Examples of inorganic fillers include fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium earth, Powders of zirconia, zircon, magnesium silicate, steatite, spinel, mullite, titanium dioxide, etc., beads obtained by spheroidizing these, glass fibers, etc. These inorganic fillers may be used alone or in combination of two or more. Among the above-mentioned inorganic fillers, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. In terms of fluidity during molding and mold wear From the standpoint of performance, the shape of the filling material is preferably spherical.

From the viewpoint of formability, reduction of thermal expansion, and improvement of strength, the content of inorganic fillers other than high dielectric constant fillers can preferably be set at 3% by mass or more to 60% by mass in 100% by mass of the thermosetting resin composition. % or less, more preferably in the range of not less than 5% by mass and not more than 50% by mass. When it is in the said range, thermal expansion reduction property and formability are excellent.

[other ingredients] The thermosetting resin composition of this embodiment can contain various components, such as a silane coupling agent, a mold release agent, a coloring agent, a dispersing agent, and a stress reducing agent, other than the said components as needed. 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 uniform mixing of the high dielectric constant filler and the inorganic filler, the miscibility of the high dielectric constant filler and organic components such as epoxy resins, and the viewpoint of bending strength/bending modulus of elasticity, it is preferable to use the etc. Use more than 2 types.

[Thermosetting resin composition] The thermosetting resin composition of the present embodiment can be produced by uniformly mixing the above-mentioned components. As a production method, there may be mentioned a method in which raw materials of a specific content are sufficiently mixed by a mixer or the like, melt-kneaded by a mixing roll, a kneader, an extruder or the like, and then cooled and pulverized. The obtained thermosetting resin composition can also be compacted in a size and quality according to the molding conditions, if necessary.

The cured product obtained from the thermosetting resin composition of this embodiment is excellent in high dielectric constant and low dielectric loss tangent in the high frequency band, so it is possible to increase the frequency, shorten the circuit, and reduce the size of high frequency devices such as communication equipment. change.

Such a thermosetting resin composition can be 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.

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, a radiation conductor plate (radiation element) 14 provided on one side of the dielectric substrate 12, and a The ground conductor plate 16 on the other side of the dielectric substrate 12 .

The shape of the radiation conductor plate includes a rectangle or a circle. In this embodiment, an example using the rectangular radiation conductor plate 14 will be described.

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

As shown in FIG. 1 , the microstrip antenna 10 of this embodiment has a radiation conductor plate 14 having a length L and a width W, and resonates at a frequency where L coincides with an integer multiple of 1/2 wavelength. When using the dielectric substrate 12 with a high dielectric constant as in the present 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 highly conductive metal such as copper, silver, and gold. Its thickness is thin enough relative to the central operating frequency of the antenna device, as long as it is about 1/50 wavelength to 1/1000 wavelength of the central operating frequency.

Examples of power supply methods for microstrip antennas include direct power supply methods such as rear coaxial power supply and coplanar power supply, and electromagnetic coupling such as slot-coupled power supply and proximity coupled power supply. Power supply (electromagnetically coupled power supply) mode.

As for the rear coaxial power supply, it is possible to supply power to the radiation conductor plate 14 from the back of the antenna using a coaxial line or a connector penetrating the ground conductor plate 16 and the dielectric substrate 12 . Regarding coplanar power supply, it is possible to supply power to the radiation conductor plate 14 through a microstrip line (not shown) disposed on the same surface as the radiation conductor plate 14 .

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

In proximity coupling power feeding, the dielectric substrate 12 has a laminated structure in which the dielectric substrate on which the radiation conductor plate 14 is formed and the dielectric substrate on which the strip conductor of the microstrip line and the ground conductor plate 16 are arranged are laminated. The radiation conductor plate 14 is excited by extending the strip conductor of the microstrip line to the lower portion of the radiation conductor plate 14 to electromagnetically couple the radiation conductor plate 14 with the microstrip line.

Other microstrip antennas are shown in FIGS. 2( a ) and 2 ( b ). In addition, the same code|symbol is attached|subjected to the same structure as FIG. 1, and description is abbreviate|omitted suitably. 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 ground conductor plate 16 provided on the other surface of the dielectric substrate 22 . And a high dielectric substrate (high dielectric) 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 the spacer 26 . The dielectric substrate 22 is formed of a low dielectric constant substrate such as a Teflon substrate. The high-dielectric substrate 24 is composed of a dielectric substrate obtained 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. Also, as shown in the microstrip antenna 20' in FIG.

＜Dielectric waveguide＞ In the present embodiment, the dielectric waveguide includes a dielectric formed by curing the thermosetting resin composition of the present embodiment, and a conductor film covering the surface of the dielectric. The dielectric waveguide transmits electromagnetic waves by confining them in a dielectric (dielectric medium). The aforementioned conductor film can be composed of a metal such as copper, an oxide high-temperature superconductor, or the like.

＜Multilayer Antenna＞ In the present embodiment, the multilayer antenna includes a dielectric sheet obtained by curing the thermosetting resin composition of the present embodiment. Specifically, a multilayer antenna is a modular one in which a circuit including a plurality of elements such as capacitors and inductors is printed on a dielectric sheet and laminated.

[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 30% by mass or more of high Dielectric constant filler (C).

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

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

In the general formula (a), when R ^a and R ^b exist in plural, they are each independently a monovalent organic group, hydroxyl group or halogen atom, r and s are each independently 0 to 4, * Indicates linkage with other atomic groups.

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

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl base, octyl, nonyl, decyl, etc. As an alkenyl group, an allyl group, a pentenyl group, a vinyl group etc. are mentioned, for example. As an alkynyl group, an ethynyl group etc. are mentioned, for example. As an alkylene group, a methylene group, an ethylene group, etc. are mentioned, for example. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl and anthracenyl. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example. As an alkaryl group, a tolyl group, a xylyl group, etc. are mentioned, for example. As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, etc. As a heterocyclic group, an epoxy group, an oxetanyl group etc. are mentioned, for example.

The total carbon numbers of the monovalent organic groups of R ^a and R ^b are, for example, 1-30, respectively, preferably 1-20, more preferably 1-10, particularly preferably 1-6.

r and s are each independently preferably 0-2, more preferably 0-1. As an example, both r and s are 0.

Regarding R ^c , when there are a plurality of them, they are each independently a monovalent organic group, a hydroxyl group, or a halogen atom, and t is an integer of 0-3. Specific examples of the monovalent organic group of R ^c include the same ones as specific examples of R ^a and R ^b . t is preferably 0-2, more preferably 0-1.

The weight average molecular weight Mw of the biphenyl aralkyl type epoxy resin of this embodiment becomes like this. Preferably it is 500-2000, More preferably, it is 600-1900, More preferably, it is 700-1800.

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

The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) use, for example, polystyrene conversion values obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions of the GPC measurement are, for example, as follows. Gel Permeation Chromatography Apparatus HLC-8320GPC manufactured by TOSOH CORPORATION Column: TSK-GEL Supermultipore HZ-M manufactured by TOSOH CORPORATION Detector: RI detector for liquid chromatography Measuring temperature: 40°C Solvent: THF Sample concentration: 2.0mg/ml

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

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

Specific examples of biphenyl epoxy resins include diglycidyl ether of 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4' - Diglycidyl ether of dihydroxybiphenyl, 3,3',5,5'-tetratertiary butyl-4,4'-diglycidyl ether of dihydroxybiphenyl, dimethyldiphenyl Diglycidyl ether of propyl biphenol and diglycidyl ether of dimethyl biphenol, etc.

The epoxy resin (A) can contain other epoxy resins other than the above-mentioned two types of epoxy resins within the range that does not impair the effects of the present invention. Examples of other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, Glycidylamine type epoxy resin, etc.

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

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

[Hardener] (B) In the present embodiment, the curing agent (B) contains an active ester-based curing agent and a phenol-based curing agent. By containing this curing agent in combination, it is possible to obtain a thermosetting resin composition capable of obtaining a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent and excellent in formability.

(active ester hardener) As the active ester-based curing agent, the same active ester compound as that described in the embodiment of the first invention can be used, and it can be produced in the same manner. In the case where the active ester hardener is a resin having a structure represented by the aforementioned general formula (1), it is preferable that "B" in the aforementioned general formula (1) is the aforementioned formula (B-1) to (B-6 ) represents the structure. The structures represented by the aforementioned formulas (B-1) to (B-6) are highly oriented structures, so when using an active ester-based hardener containing this structure, the obtained thermosetting resin composition The cured product has a low dielectric loss tangent and is excellent in adhesion to metal, so it can be suitably used as a semiconductor sealing material.

Also, when the total number of arylcarbonyloxy groups and phenolic hydroxyl groups in the resin structure is used as the number of functional groups of the resin, it is possible to obtain a cured product with excellent curability and a low dielectric loss tangent. The functional group equivalent weight of the active ester hardener is preferably in the range of not less than 200 g/eq and not more than 230 g/eq, more preferably in the range of not less than 210 g/eq and not more than 220 g/eq.

In the thermosetting resin composition of this embodiment, from the viewpoint of obtaining a cured product having excellent curability and a low dielectric loss tangent, the blending amounts of the active ester-based curing agent and the epoxy resin are preferably as follows Ratio: The epoxy group in the epoxy resin) is 0.8 to 1.2 equivalents with respect to 1 equivalent of the total active groups in the active ester-based hardener. Here, the active group in the active ester hardener refers to the aryl carbonyloxy group and the phenolic hydroxyl group in the resin structure.

In the composition of this embodiment, the active ester-based curing agent is preferably at least 0.2% by mass and not more than 15% by mass, more preferably at least 0.5% by mass and not more than 10% by mass, with respect to the entire thermosetting resin composition. Preferably, it is used in an amount of not less than 1.0% by mass and not more than 7% by mass. By containing the specific active ester-based curing agent within the above range, the obtained cured product can have more excellent dielectric properties, and the low dielectric loss tangent is further excellent.

The resin composition according to this embodiment is further excellent in high dielectric constant and low dielectric loss tangent by using an active ester-based hardener in combination with a high dielectric constant filler described later, and these effects are excellent even in high frequency bands. From the viewpoint of the above-mentioned effects, the active ester-based hardener can be contained as follows: preferably at least 1 part by mass and at most 30 parts by mass, more preferably 2 parts by mass with respect to 100 parts by mass of the high dielectric constant filler described later The above is 20 mass parts or less, and more preferably 3 mass parts or more and 15 mass parts or less.

In addition, as described in JP-A-2020-90615, the present applicant disclosed a resin composition containing an epoxy resin and a specific active ester-based hardener in a semiconductor sealing application different from the present invention. The present invention differs from the technology described in JP 2020-90615 A in that it contains a high dielectric constant filler. In addition, since it contains a high dielectric constant filler, the effect based on the combination of active ester hardener and epoxy resin is also in terms of high dielectric constant, high dielectric constant and low dielectric loss in the high frequency band Tangent excels in different ways.

(phenolic hardener) Examples of phenolic hardeners include phenol novolak resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, naphthol arane Base resin, Trimethylol methane resin, Tetraphenol-based ethane resin, Naphthol novolac resin, Naphthol-phenol co-phenol novolak resin, Naphthol-cresol co- novolak resin, Biphenyl modified phenol resin (polyhydric phenolic compound with phenol nucleus linked by double methylene groups), biphenyl modified naphthol resin (polyhydric naphthol compound with phenolic nucleus linked by double methylene), amino tri-methanol modified Polyphenolic compounds such as phenolic resins (polyphenolic compounds in which phenolic nuclei are linked by melamine, benzoguanamine, etc.).

The blending amount of the phenolic curing agent is preferably an amount of not less than 20% by mass and not more than 70% by mass 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 hardener b to the active ester hardener a (b (parts by mass)/a (parts by mass)) can be preferably set to 0.5 to 8, more preferably 1 to 5, and even more preferably It is better to set it as 1.5 or more and 3 or less. By containing the active ester-based curing agent and the phenol-based curing agent in the above-mentioned ratio, the obtained cured product can have more excellent dielectric properties, and the low dielectric loss tangent is further excellent.

In the composition of this embodiment, the curing agent (B) containing an active ester-based curing agent and a phenol-based curing agent is preferably at least 0.2% by mass and not more than 15% by mass, more preferably at most 15% by mass, based on the entire thermosetting resin composition. It is used in an amount of not less than 0.5% by mass and not more than 10% by mass, more preferably not less than 1.0% by mass and not more than 7% by mass. By containing the specific active ester-based curing agent within the above range, the obtained cured product can have more excellent dielectric properties, and the low dielectric loss tangent is further excellent.

[High dielectric constant filler (C)] In this embodiment, examples of the high dielectric constant filler (C) include calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, titanate Zirconium, zinc titanate, barium zirconate, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, calcium zirconate, and the like can contain at least one selected from these. By containing such 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 effect of the present invention, as the high dielectric constant filler, preferably at least one selected from calcium titanate, strontium titanate and magnesium titanate, and more preferably selected from calcium titanate and At least one kind of magnesium titanate.

The shape of the high dielectric constant filler is granular, amorphous, flaky, etc., and the high dielectric constant filler of these shapes can be used in any proportion. From the viewpoint of the effects of the present invention and fluidity/fillability, the average particle diameter of the high dielectric constant filler is preferably from 0.1 μm to 50 μm, more preferably from 0.3 μm to 20 μm, and still more preferably from 0.5 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, 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 less. When the added amount of the high dielectric constant filler is within the above-mentioned range, the obtained cured product has a lower dielectric constant and is also excellent in the production of molded products.

[Hardening Catalyst (D)] The thermosetting resin composition of the present embodiment may further contain a curing catalyst (D). The curing catalyst (D) may also be called a curing accelerator or the like. The curing catalyst (D) is not particularly limited as long as it accelerates the curing reaction of the thermosetting resin, and known curing catalysts can be used.

Specific examples of the curing catalyst (D) include organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and addition products of phosphonium compounds and silane compounds. Phosphorous atom-containing compounds such as compounds; 2-methylimidazole, 2-phenylimidazole and other imidazoles (imidazole hardening accelerators); 1,8-diacricyclo[5.4.0]undecene-7, benzyldi Nitrogen atom-containing compounds such as amidines or tertiary amines, quaternary salts of amidines or amines exemplified by methylamine, etc., may be used alone or in combination of two or more.

Among them, from the viewpoint of improving hardenability and obtaining a magnetic material excellent in mechanical strength such as bending strength, it is preferable to contain a phosphorus atom-containing compound, and it is more preferable to contain a tetrasubstituted phosphonium compound, a phosphobetaine compound, or a phosphine compound. Those with latent properties such as adducts of quinone compounds, adducts of phosphonium compounds and silane compounds, especially tetrasubstituted phosphonium compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds .

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

Examples of organic phosphines include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine tertiary phosphine such as base phosphine. As a tetrasubstituted phosphonium compound, the compound etc. which are represented by following General formula (6) are mentioned, for example.

In the 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 an aromatic ring.

AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group 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. Firstly, tetrasubstituted phosphonium halides, aromatic organic acids and bases are added to an organic solvent and mixed uniformly to generate aromatic organic acid anions in the solution system. Next, when water is added, the compound represented by the general formula (6) can be precipitated. Among the compounds represented by the general formula (6), it is preferable that 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 an aromatic ring, that is, phenols , and A is the anion of the phenol. Examples of the above-mentioned phenols include monocyclic phenols such as phenol, cresol, resorcinol, and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthracene diol; Bisphenols such as phenol F and bisphenol S, polycyclic phenols such as phenylphenol and biphenol, etc.

As a phosphobetaine compound, the compound etc. which are represented by following General formula (7) are mentioned, for example.

In the 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, it is obtained through the step of contacting a triaromatic substituted phosphine which is a tertiary phosphine with a diazonium salt to replace the diazonium group possessed by the triaromatic substituted phosphine and the diazonium salt.

As an adduct of a phosphine compound and a quinone compound, the compound etc. which are represented by following General formula (8) are mentioned, for example.

In the general formula (8), P represents a phosphorus atom. R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group having 1 to 12 carbons or an aryl group having 6 to 12 carbons, and may be the same as or different from each other.

R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbons, and may be the same as or different from each other, and R ¹⁴ and R ¹⁵ may be bonded to form a ring structure.

As the phosphine compound used for the adduct of a phosphine compound and a quinone compound, for example, triphenylphosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, trinaphthylphosphine, tri( Benzyl) phosphine or the like has no substitution in the aromatic ring or has a substituent such as an alkyl group or an alkoxy group. Examples of the substituent such as an alkyl group or an alkoxy group include those having a carbon number of 1 to 6. From the viewpoint of easy availability, triphenylphosphine is preferred.

Moreover, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include benzoquinone and anthraquinones, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing them in a solvent capable of dissolving both the organic tertiary phosphine and the benzoquinone. As a solvent, among ketones, such as acetone and methyl ethyl ketone, those with low solubility to an adduct are preferable. However, it is not limited to this.

Among the compounds represented by the general formula (8), R ¹⁰ , R ¹¹ and R ¹² bonded to the phosphorus atom are phenyl groups, and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, namely: 1 , The compound obtained by adding 4-benzoquinone and triphenylphosphine is preferable in terms of reducing the thermal elastic modulus of the cured product of the resin composition for sealing.

As an adduct of a phosphonium compound and a silane compound, the compound etc. which are represented by following General formula (9) are mentioned, for example.

In the 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 or aliphatic group having an aromatic ring or a heterocyclic ring, and may be the same or different from each other. R ²⁰ is an organic group bonded to groups Y ² and Y ³ . R ²¹ is an organic group bonded to groups Y ⁴ and Y ⁵ .

Y ² and Y ³ represent groups formed by releasing protons from a proton donating group, and the groups Y ² and Y ³ in the same molecule are bonded to silicon atoms to form a chelate structure.

Y ⁴ and Y ⁵ represent groups formed by releasing a proton from a protic group, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded 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 or aliphatic group having an aromatic ring or a heterocyclic ring.

In the general formula (9), examples of R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl, and hydroxynaphthyl. , benzyl, methyl, ethyl, n-butyl, n-octyl, and cyclohexyl, among others, more preferably phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, and hydroxynaphthyl A substituted or unsubstituted aromatic group such as an alkyl group, an alkoxy group, a hydroxyl group, etc.

In the general formula (9), R ²⁰ is an organic group bonded to Y ² and Y ³ . Likewise, R ²¹ is an organic group bonded to groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by releasing a proton from a protic group, and the groups Y ² and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups that release a proton from a protic group, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same as or different from each other, and the groups Y ² , Y ³ , Y ⁴ and Y ⁵ 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 the general formula (9) are those formed by releasing two protons from the proton donor, as The proton donor is preferably an organic acid with at least 2 carboxyl groups or hydroxyl groups in the molecule, and more preferably an aromatic compound with at least 2 carboxyl groups or hydroxyl groups on the adjacent carbons constituting the aromatic ring, more preferably in An aromatic compound having at least two hydroxyl groups on adjacent carbons constituting an aromatic ring, for example, catechol, gallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2' -Biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloronic acid, tannic acid, 2-hydroxybenzyl Alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerol, etc., but among them, catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene are more preferable .

Z in the general formula ( ⁹ ) represents an organic or aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include methyl, ethyl, propyl, butyl, hexyl, and octyl Aliphatic hydrocarbon groups, phenyl, benzyl, naphthyl and biphenyl and other aromatic hydrocarbon groups, glycidoxypropyl, mercaptopropyl, aminopropyl, etc. have glycidoxy, mercapto, amino groups Among them, methyl, ethyl, phenyl, naphthyl and biphenyl are more preferable in terms of thermal stability. A method for producing an adduct of a phosphonium compound and a silane compound is, for example, as follows.

Add silane compounds such as phenyltrimethoxysilane and proton donors such as 2,3-dihydroxynaphthalene to a flask filled with methanol and dissolve them, then add sodium methoxide-methanol solution dropwise while stirring at room temperature. Furthermore, when the solution which melt|dissolved tetra-substituted phosphonium halides, such as tetraphenylphosphonium bromide, prepared previously in methanol was dripped there, with stirring at room temperature, a crystal|crystallization will precipitate. The adduct of phosphonium compound and silane compound can be obtained by filtering the precipitated crystal, washing it with water and drying it in vacuum.

When using a hardening catalyst (D), its content is preferably 0.1-3 mass % with respect to 100 mass % of thermosetting resin compositions, More preferably, it is 0.3-2 mass %. By setting it as such a numerical value range, the hardening acceleration effect can fully be acquired, without deteriorating other performance too much.

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

Examples of inorganic fillers include fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium earth, Powders of zirconia, zircon, magnesium silicate, steatite, spinel, mullite, titanium dioxide, etc., beads obtained by spheroidizing these, glass fibers, etc. These inorganic fillers may be used alone or in combination of two or more. Among the above-mentioned inorganic fillers, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. In terms of fluidity during molding and mold wear From the standpoint of performance, the shape of the filling material is preferably spherical.

From the viewpoint of formability, thermal expansion reduction, and strength improvement, the amount of inorganic fillers other than the high dielectric constant filler (C) can be preferably set relative to 100% by mass of the thermosetting resin composition. It is in the range of 10 mass % to 50 mass %, more preferably 15 mass % to 40 mass %, further preferably 20 mass % to 35 mass %. When it is in the said range, thermal expansion reduction property and formability are excellent.

[other ingredients] The thermosetting resin composition of this embodiment can contain various components, such as a silane coupling agent, a mold release agent, a coloring agent, a dispersing agent, and a stress reducing agent, other than the said components as needed.

The thermosetting resin composition of this embodiment contains the following epoxy resin (A), the following curing agent (B) and the following high dielectric constant filler (C), and contains 30% of the composition in 100% by mass. High dielectric constant filler (C) at mass % or more. Epoxy resin (A): Contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin. Hardener (B): Contains an active ester-based hardener and a phenolic hardener. High dielectric constant filler (C): containing calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, zirconium At least one of barium oxide, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate, and calcium zirconate. According to the thermosetting resin composition of the present embodiment obtained by combining such components, it is possible to obtain a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent, and further, it is possible to provide a Microstrip antenna.

The thermosetting resin composition of the present embodiment can be preferably 2 mass % to 30 mass % in 100 mass % of the composition, more preferably 3 mass % to 25 mass %, and more preferably 5 mass % % to 20% by mass contains epoxy resin (A), Curing can be contained in an amount of preferably 0.2 mass % to 15 mass %, more preferably 0.5 mass % to 10 mass %, further preferably 1.0 mass % to 7 mass % in 100 mass % of the composition. agent (B), The high dielectric constant filler (C) can be contained at 30% by mass or more, preferably at least 35% by mass, more preferably at least 45% by mass in 100% by mass of the composition. The upper limit is 80% by mass.

In this embodiment, 30% by mass or more of high dielectric constant filler (C) is contained in 100% by mass of the composition by combining epoxy resin (A), hardener (B) and high dielectric constant filler (C). The constant filler (C) can provide a thermosetting resin composition capable of obtaining a dielectric substrate having a higher dielectric constant and a lower dielectric loss tangent.

The thermosetting resin composition of this embodiment can be manufactured by uniformly mixing the above-mentioned components. As a production method, there may be mentioned a method of sufficiently mixing raw materials of a specified blending amount by a mixer or the like, melting and kneading by a mixing roll, a kneader, an extruder, and the like, followed by cooling and pulverization. The obtained thermosetting resin composition can also be compacted in a size and quality according to molding conditions, if necessary.

In the thermosetting resin composition of the present embodiment, the flow length of the spiral flow is 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 is excellent in formability.

The spiral flow test can be performed, for example, by using a low-pressure transfer molding machine ("KTS-15" manufactured by KOHTAKI Corporation.) under the conditions of a mold temperature of 175°C, an injection pressure of 6.9MPa, and a curing time of 120 seconds. Inject the resin molding material downward into the mold for measuring spiral flow according to EMMI-1-66, and measure the flow length.

The gel time of the thermosetting resin composition of this embodiment is preferably from 32 seconds to 80 seconds, more preferably from 35 seconds to 70 seconds. When the gel time of the thermosetting resin composition is not less than the above-mentioned lower limit, the fillability is excellent, and when it is not more than the above-mentioned upper limit, the formability becomes good.

In addition, in the thermosetting resin composition of this embodiment, the rectangular pressure measured under the following conditions is 0.1 MPa or more, preferably 0.15 MPa or more, and more preferably 0.20 MPa or more. Rectangular pressure is a parameter of melt viscosity, the smaller the value, the lower the melt viscosity. The thermosetting resin composition of the present embodiment is excellent in mold fillability during molding because the rectangular pressure is within the above-mentioned range.

(Conditions) Using a low-pressure transfer molding machine, inject a thermosetting resin composition into a rectangular channel with a width of 13mm, a thickness of 1mm, and a length of 175mm under the conditions of a mold temperature of 175°C and an injection speed of 177mm ³ /sec. , by measuring the change over time of the pressure with a pressure sensor buried at a position 25 mm from the upstream front end of the flow path, the minimum pressure when the aforementioned thermosetting resin composition flows is calculated, and the minimum pressure is regarded as the rectangular pressure.

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

The cured product obtained from the thermosetting resin composition of this embodiment is excellent in high dielectric constant and low dielectric loss tangent in the high frequency band, so it is possible to increase the frequency, shorten the circuit, and reduce the size of communication equipment, etc. , can be suitably used as a material for forming a microstrip antenna, a material for forming a dielectric waveguide, and a material for forming an electromagnetic wave absorber.

＜Microstrip Antenna＞ Similar to the embodiment of the first invention, since the microstrip antenna of this embodiment has the configuration shown in FIG. 1 , FIG. 2( a ), and FIG. 2( b ), description thereof will be omitted.

＜Dielectric waveguide＞ In the present embodiment, the dielectric waveguide includes a dielectric formed by curing the thermosetting resin composition of the present embodiment, and a conductor film covering the surface of the dielectric. The dielectric waveguide transmits electromagnetic waves by confining them in a dielectric (dielectric medium). The aforementioned conductor film can be composed of a metal such as copper, an 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. This electromagnetic wave absorber can be used as a λ/4 type radio wave absorber having high radio wave absorbing performance. A resin base material etc. are mentioned as a support body. The resistance film can be protected by the support, and the durability as a radio wave absorber can be improved. Examples of the resistor film include those containing indium tin oxide and molybdenum. 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 reflective layer for radio waves, and examples thereof include metal films.

As mentioned above, although embodiment of this invention was described, these are examples of this invention, Various structures other than the above can be used in the range which does not impair the effect of this invention. [Example]

Hereinafter, the present invention will be described in further detail based on examples, but the present invention is not limited thereto. Examples of the first invention (claims 1 to 13 and 22 to 24 at the time of application) and the first embodiment are shown in Example A. Examples of the second invention (claims 14-21, 22-24 at the time of application) and the second embodiment are shown in Example B.

<Example A> [Examples A1 to A4, Comparative Example A1] ＜Preparation of Thermosetting Resin Composition＞ The following raw materials were mixed using a mixer at room temperature at the contents shown in Table 1, and then roll kneaded at 70 to 100°C. Next, after cooling the obtained kneaded product, it was pulverized to obtain a powdery thermosetting resin composition. Next, an ingot-shaped thermosetting resin composition was obtained by ingot molding under high pressure.

Hereinafter, the information of the raw material in Table 1 is shown. (High dielectric constant filler) ・High dielectric constant filler 1: Calcium titanate (CT, average particle size: 2.0 μm, manufactured by Fuji Titanium Industry Co., Ltd., specific permittivity at 25°C, 1GHz: 135)

(inorganic filler material) ・Inorganic filler 1: Alumina (K75-1V25F, manufactured by Denka Company Limited.) ・Inorganic filler 2: Fused spherical silica (SC-2500-SQ, manufactured by Admatechs Company Limited)

(thermosetting resin) ・Epoxy resin 1: Biphenyl type epoxy resin (YX4000K, manufactured by Mitsubishi Chemical Corporation.) ・Epoxy resin 2: Phenyl aralkyl type epoxy resin containing biphenylene skeleton (NC3000L, manufactured by Nippon Kayaku Co., Ltd.) ・Epoxy resin 3: Bisphenol A type epoxy resin (YL6810, manufactured by Mitsubishi Chemical Corporation.)

(Active ester compound) ・Active ester compound 1: Active ester compound prepared by the following preparation method. Put biphenyl-4,4 in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer 279.1 g of '-dicarboxylic acid dichloride (number of moles of the amide chloride group: 2.0 moles) and 1338 g of toluene were dissolved by substituting nitrogen under reduced pressure inside the system. Next, 96.5 g of α-naphthol (0.67 moles) and 219.5 g of dicyclopentadienol resin (the number of moles of phenolic hydroxyl groups: 1.33 moles) were charged, and the inside of the system was replaced with nitrogen under reduced pressure to make it dissolve. Thereafter, 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to be below 60° C. while purging nitrogen. Next, stirring was continued for 1.0 hour under the conditions. After the reaction was completed, the mixture was left still for liquid separation, and the water layer was removed. Furthermore, water was poured into the toluene phase in which the reactants were dissolved, stirred and mixed for about 15 minutes, and the water layer was removed by standing still for liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration with a decanter to obtain an active ester resin in a toluene solution state having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it has a structure in which R ¹ and R ³ are hydrogen atoms, Z is naphthyl, and l is 0 in the above formula (1-1). Furthermore, the average value k of the repeating unit is in the range of 0.5 to 1.0 as a result of calculation based on the reaction equimolar ratio.

・Active ester compound 2: The active ester compound prepared by the following preparation method is filled with 1,3-benzenedicarboxylic acid diamide chloride in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer 203.0 g (number of moles of amide chloride group: 2.0 moles) and 1338 g of toluene were dissolved by substituting nitrogen under reduced pressure inside the system. Next, 96.5 g of α-naphthol (0.67 moles) and 219.5 g of dicyclopentadienol resin (the number of moles of phenolic hydroxyl groups: 1.33 moles) were charged, and the inside of the system was replaced with nitrogen under reduced pressure to make it dissolve. Thereafter, 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to be below 60° C. while purging nitrogen. Next, stirring was continued for 1.0 hour under the conditions. After the reaction was completed, the mixture was left still for liquid separation, and the water layer was removed. Furthermore, water was poured into the toluene phase in which the reactants were dissolved, stirred and mixed for about 15 minutes, and the water layer was removed by standing still for liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration with a decanter to obtain an active ester resin in a toluene solution state with a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it has 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 is in the range of 0.5 to 1.0 based on the result calculated from the reaction equimolar ratio. Specifically, the obtained active ester resin has a structure represented by the following chemical formula. In the following formulae, the average value k of the repeating unit is 0.5 to 1.0.

(hardener) ・Phenolic hardener 1: Biphenyl aralkyl type resin (HE910-20, manufactured by AIR WATER INC.) ・Phenolic hardener 2: Phenyl aralkyl type resin containing biphenylene skeleton (MEH-7851SS, manufactured by MEIWA PLASTIC INDUSTRIES, LTD.)

(silane coupling agent) ・Silane coupling agent 1: Anilinopropyltrimethoxysilane (CF4083, manufactured by Dow Corning Toray Co., Ltd.) ・Silane coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sila-Ace, manufactured by JNC Corporation)

(hardening catalyst) ・Curing catalyst 1: Tetraphenylphosphonium-4,4’-sulfonyl diphenolate ・Hardening catalyst 2: Tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenylsilicate

(release agent) ・Release agent 1: Glycerol trimontanate (Licolub WE-4, manufactured by Clariant Japan K.K.)

(Evaluation of dielectric constant and dielectric loss tangent obtained by cavity resonator method) The obtained thermosetting resin composition was coated on a Si substrate, and prebaked at 120°C for 4 minutes to form a coating A resin film with a film thickness of 12 μm. This was heated in an oven at 200° C. for 90 minutes under a nitrogen atmosphere, and subjected to a hydrofluoric acid treatment (immersion in a 2 mass % hydrofluoric acid aqueous solution). After taking out the board|substrate from hydrofluoric acid, the cured film was peeled off from the Si board|substrate, and this was made into the test piece. As the measuring device, Network Analyzer HP8510C, Synthesized sweeper HP83651A, and test set HP8517B (all manufactured by Agilent Technologies Japan, Ltd.) were used. These devices and a cylindrical cavity resonator (with an inner diameter of φ42mm and a height of 30mm) were installed. The resonant frequency, 3dB bandwidth, penetration power ratio, etc. were measured at a frequency of 18 GHz with the test piece inserted into the resonator and in the uninserted state. Thereafter, the measurement results were analytically calculated by software, thereby obtaining the dielectric properties of the dielectric constant (Dk) and dielectric loss tangent (Df). Also, set the measurement mode to TE ₀₁₁ mode.

(glass transition temperature, coefficient of linear expansion) The glass transition temperature (Tg) and coefficient of linear expansion (CTE1, CTE2) of the cured product of the obtained thermosetting resin composition were measured as follows. First, using a low-pressure transfer molding machine ("KTS-15" manufactured by KOHTAKI Corporation.), under the conditions of a mold temperature of 175°C, an injection pressure of 6.9MPa, and a curing time of 120 seconds, a thermosetting resin for sealing was formed. The material was injection molded to obtain a test piece of 10mm×4mm×4mm. Next, after post-hardening the obtained test piece at 175°C for 4 hours, use a thermomechanical analysis device (manufactured by Seiko Instruments & Electronics Ltd., TMA100) to measure the temperature in the range of 0°C to 320°C and the temperature increase rate at 5°C /min were measured. Based on the measurement results, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) are calculated.

(Evaluation of mechanical strength (bending strength, flexural modulus)) Using a low-pressure transfer molding machine ("KTS-30" manufactured by KOHTAKI Corporation.), at a mold temperature of 130°C, an injection pressure of 9.8MPa, and a curing time of 300 Inject the obtained thermosetting resin composition into the mold under the condition of seconds. Thereby, a molded product having 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-hardened at 175° C. for 4 hours. Thereby, the test piece for evaluation of mechanical strength was produced. Then, according to JIS K 6911, the flexural strength (N/mm ² ) and flexural modulus (N/mm ² ) of the test piece were measured at room temperature (25°C) or 260°C at a crosshead speed of 5 mm/min. .

[Table 1] unit Example A1 Example A2 Example A3 Example A4 Comparative Example A1 High dielectric constant filler High dielectric constant filler 1 quality% 54 54 54 54 twenty four Inorganic Filler Inorganic filler material 1 15 18 15 15 61 Inorganic filler material 2 15 17 15 15 epoxy resin epoxy resin 1 3 2 3 3 3.48 Epoxy 2 4.5 3.5 4.5 4.5 2.3 Epoxy 3 0.8 hardener Phenolic hardener 1 1 1 1 Phenolic hardener 2 1 1 active ester compound Active ester compound 1 6 3 6 6 Active ester compound 2 6 Silane coupling agent Silane coupling agent 1 0.1 0.1 0.1 0.1 0.2 Silane coupling agent 2 0.2 0.2 0.2 0.2 hardening catalyst Hardening Catalyst 1 0.15 0.15 0.15 0.15 0.17 Hardening Catalyst 2 0.85 0.85 0.85 0.85 0.85 Release agent Release agent 1 0.2 0.2 0.2 0.2 0.2 total 100 100 100 100 100 Dielectric constant 9.5 9.5 9.5 9.5 9.5 Dielectric loss tangent 0.0053 0.0052 0.0052 0.0051 0.0065 CTE1 PPm 20 15 twenty one twenty one - CTE2 ppm 81 64 78 83 - Tg ℃ 111 141 114 114 - Flexural strength at 25°C (FS ₂₅ ) N/ ^mm2 101 128 126 105 100 Flexural Modulus of Elasticity at 25°C (FM ₂₅ ) N/ ^mm2 22139 28865 20825 23138 27000 260°C Bending Strength (FS ₂₆₀ ) N/ ^mm2 5 6 5 5 2 Flexural Modulus of Elasticity at 260°C (FM ₂₆₀ ) N/ ^mm2 199 501 157 211 86 FM ₂₆₀ /FM ₂₅ 0.009 0.017 0.008 0.009 0.003 FS ₂₆₀ /FS ₂₅ 0.045 0.046 0.036 0.048 0.020 Durability in heat ○ ○ ○ ○ x

(durability when hot) Regarding the obtained cured product of the thermosetting resin composition, the rate of change in physical properties after applying a heat history at 175° C. for 100 hours was repeated 10 times was evaluated. When the flexural modulus at 260°C before the thermal history before repeated application is FMa, and the flexural modulus at 260°C before the thermal history after repeated application is FMb, the formula (FMa-FMb)/FMa× When the rate of change obtained from 100% was within 200%, it was evaluated as ◯, and when it exceeded 200%, it was evaluated as ×.

The thermosetting resin compositions of Examples A1 to A4 of the first invention show that they can form members that are excellent in high dielectric constant and low dielectric loss tangent in the high frequency band and have excellent thermal durability compared with Comparative Example A1 (cured matter) results. Such a thermosetting resin composition can be suitably used to form a part of high-frequency devices such as microstrip antennas, dielectric waveguides, and multilayer antennas.

<Example B> [Examples B1 to B10, Comparative Example B1] The following raw materials were mixed using a mixer at room temperature in the blending amounts shown in Table 2, and then roll kneaded at 70 to 100°C. Next, after cooling the obtained kneaded product, it was pulverized to obtain a powdery resin composition. Next, an ingot-shaped resin composition was obtained by performing ingot 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: Aluminum oxide (DAB25MA-TS3, manufactured by Denka Company Limited.) ・Inorganic filler 2: Fused spherical silica (SC-2500-SQ, manufactured by Admatechs Company Limited)

(Colorant) ・Color 1: Black titanium oxide (manufactured by AKO KASEI CO., LTD.)

(coupling agent) ・Coupling agent 1: Anilinopropyltrimethoxysilane (CF-4083, manufactured by Dow Corning Toray Co., Ltd.) ・Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Sila-Ace, manufactured by JNC Corporation)

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

(Curing agent) ・Curing agent 1: Active ester-based curing agent prepared by the following production method (preparation method of active ester-based curing agent) 279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride (the number of moles of the amide chloride group: 2.0 moles) and 1338 g of toluene were placed in the flask, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. Next, 96.5 g of α-naphthol (0.67 moles) and 219.5 g of dicyclopentadienol resin (the number of moles of phenolic hydroxyl groups: 1.33 moles) were charged, and the inside of the system was replaced with nitrogen under reduced pressure to make it dissolve. Thereafter, 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to be below 60° C. while purging nitrogen. Next, stirring was continued for 1.0 hour under the conditions. After the reaction was completed, the mixture was left still for liquid separation, and the water layer was removed. Furthermore, water was poured into the toluene phase in which the reactants were dissolved, stirred and mixed for about 15 minutes, and the water layer was removed by standing still for liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration with a decanter to obtain an active ester resin in a toluene solution state having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it has a structure in which R ¹ and R ³ are hydrogen atoms, Z is naphthyl, and l is 0 in the above formula (1-1). Furthermore, the average value k of the repeating unit is in the range of 0.5 to 1.0 as a result of calculation based on the reaction equimolar ratio.・Hardener 2: Phenol aralkyl type resin containing biphenylene skeleton (MEH-7851SS, manufactured by MEIWA PLASTIC INDUSTRIES, LTD.) ・Hardener 3: Phenol hydroxybenzaldehyde type hardener (MEH-7500, manufactured by MEIWA PLASTIC Industries, Ltd.) ・Hardener 4: Novolak-type phenol resin (Sumilite Resin PR-51470, manufactured by Sumitomo Bakelite Co., Ltd.) ・Hardener 5: Aralkylphenol-type phenol Aralkyl-type phenol hardener (MEHC-7800SS, manufactured by MEIWA PLASTIC INDUSTRIES, LTD.) ・Hardener 6: Polyvalent MAR type phenol hardener (SH-002-02, manufactured by MEIWA PLASTIC INDUSTRIES, LTD.) ・Hardener 7: Prepared by the following Active ester-based hardener prepared by method (preparation method of active ester-based hardener) Put 1,3-benzenedicarboxylic acid diamide into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer 203.0 g of chlorine (the number of moles of the acetyl chloride group: 2.0 moles) and 1338 g of toluene were dissolved by replacing the inside of the system with nitrogen under reduced pressure. Next, 96.5 g of α-naphthol (0.67 moles) and 219.5 g of dicyclopentadienol resin (the number of moles of phenolic hydroxyl groups: 1.33 moles) were charged, and the inside of the system was replaced with nitrogen under reduced pressure to make it dissolve. Thereafter, 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to be below 60° C. while purging nitrogen. Next, stirring was continued for 1.0 hour under the conditions. After the reaction was completed, the mixture was left still for liquid separation, and the water layer was removed. Furthermore, water was poured into the toluene phase in which the reactants were dissolved, stirred and mixed for about 15 minutes, and the water layer was removed by standing still for liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration with a decanter to obtain an active ester resin in a toluene solution state having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, it has 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 is in the range of 0.5 to 1.0 based on the result calculated from the reaction equimolar ratio. Specifically, the obtained active ester resin has a structure represented by the following chemical formula. In the following formulae, the average value k of the repeating unit is 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 coated on Si substrates, and prebaked at 120° C. for 4 minutes to form a resin film with a thickness of 12 μm. This was heated in an oven at 200° C. for 90 minutes under a nitrogen atmosphere, and subjected to a hydrofluoric acid treatment (immersion in a 2 mass % hydrofluoric acid aqueous solution). After taking out the board|substrate from hydrofluoric acid, the cured film was peeled off from the Si board|substrate, and this was made into the test piece. As the measuring device, Network Analyzer HP8510C, Synthesized sweeper HP83651A, and test set HP8517B (all manufactured by Agilent Technologies Japan, Ltd.) were used. These devices and a cylindrical cavity resonator (with an inner diameter of φ42mm and a height of 30mm) were installed. The resonant frequency, 3dB bandwidth, penetration power ratio, etc. were measured at a frequency of 25 GHz with the test piece inserted into the resonator and in the uninserted state. Thereafter, the measurement results were analytically calculated by software, thereby obtaining the dielectric properties of the dielectric constant (Dk) and dielectric loss tangent (Df). Also, set the measurement mode to TE ₀₁₁ mode.

(measurement of spiral flow) Using a low-pressure transfer molding machine ("KTS-15" manufactured by KOHTAKI Corporation.), under the conditions of a mold temperature of 175°C, an injection pressure of 6.9MPa, and a hardening time of 120 seconds, spiral flow according to EMMI-1-66 The resin compositions obtained in Examples and Comparative Examples were poured into measurement molds, and the flow lengths were measured.

(Gel time (GT)) After melting the resin compositions of Examples and Comparative Examples on a hot plate heated to 175° C., the time (unit: second) until hardening was measured while kneading with a spatula.

(Molding shrinkage) Regarding the respective examples and comparative examples, the molding shrinkage (after ASM) of the obtained resin composition after molding (ASM: as Mold) was measured, and after assuming the molding, it was hardened to produce a dielectric body Molding shrinkage (after PMC) was evaluated under the substrate heating conditions (PMC: Post Mold Cure (post-cure)). First, for a test piece manufactured using a low-pressure transfer molding machine ("KTS-15" manufactured by KOHTAKI Corporation.) under the conditions of a mold temperature of 175°C, an injection pressure of 6.9MPa, and a curing time of 120 seconds, JIS K 6911 was followed. Forming shrinkage (after ASM) was obtained. Furthermore, the obtained test piece was heat-processed at 175 degreeC for 4 hours, and the mold shrinkage rate (after ASM) was measured based on JISK6911.

(glass transition temperature, coefficient of linear expansion) Regarding each of the Examples and Comparative Examples, the glass transition temperature (Tg) and linear expansion coefficient (CTE1, CTE2) of the cured product of the obtained resin composition were measured in the following manner. First, the resin composition for sealing was injected and molded using a low-pressure transfer molding machine ("KTS-15" manufactured by KOHTAKI Corporation.) at a mold temperature of 175°C, an injection pressure of 6.9MPa, and a curing time of 120 seconds. A test piece of 10 mm×4 mm×4 mm was obtained. Next, after post-hardening the obtained test piece at 175°C for 4 hours, use a thermomechanical analysis device (manufactured by Seiko Instruments & Electronics Ltd., TMA100) to measure the temperature in the range of 0°C to 320°C and the temperature increase rate at 5°C /min were measured. Based on the measurement results, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) are calculated.

(Evaluation of Mechanical Strength (Bending Strength/Bending Elastic Modulus)) Using a low-pressure transfer molding machine ("KTS-30" manufactured by KOHTAKI Corporation.), at a mold temperature of 130°C, an injection pressure of 9.8MPa, and a curing time of 300 The resin compositions of Examples and Comparative Examples were injection-molded into molds under the condition of seconds. Thereby, a molded product having 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-hardened at 175° C. for 4 hours. Thereby, the test piece for evaluation of mechanical strength was produced. Then, according to JIS K 6911, the flexural strength (N/mm ² ) and flexural modulus (N/mm ² ) of the test piece were measured at room temperature (25°C) or 260°C at a crosshead speed of 5 mm/min. .

[Table 2] Comparative Example B1 Example B1 Example B2 Example B3 Example B4 Example B5 Example B6 Example B7 Example B8 Example B9 Example B10 High dielectric constant filler High dielectric constant filler 1 (parts by mass) 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 Inorganic filler Inorganic filler 1 27.50 27.50 27.50 27.50 27.50 27.50 27.50 27.50 27.50 27.50 27.50 Inorganic filler 2 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Colorant Colorant 1 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Coupler Coupler 1 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Coupler 2 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 epoxy resin epoxy resin 1 9.68 9.68 9.68 9.68 9.68 9.68 9.68 9.68 9.68 9.68 9.68 hardener Hardener 1 2.39 2.39 2.39 2.39 2.39 Hardener 2 7.19 4.79 4.79 Hardener 3 4.79 4.79 Hardener 4 4.79 4.79 Hardener 5 4.79 4.79 Hardener 6 4.79 4.79 Hardener 7 2.39 2.39 2.39 2.39 2.39 catalyst Catalyst 1 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 total (parts by mass) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Dielectric constant (Dk) 25GHz 14.1 13.9 13.9 13.9 13.9 13.9 14.0 14.0 13.9 13.9 14.0 Dielectric loss tangent (Df) 25GHz 0.0456 0.0115 0.0118 0.0116 0.0115 0.0113 0.0107 0.0111 0.0109 0.0115 0.0114 spiral flow cm 90 137 126 130 128 100 129 122 128 119 92 Gel time (GT) sec. 30 51 51 48 49 40 48 50 49 50 39 Forming shrinkage ASM % 0.62 0.62 0.57 0.60 0.57 0.57 0.63 0.55 0.62 0.56 0.57 PMC % 0.62 0.62 0.56 0.60 0.57 0.60 0.62 0.56 0.61 0.56 0.55 Linear expansion coefficient CTE1 ppm/°C twenty one twenty one 20 20 twenty one 20 twenty one twenty one 20 twenty one twenty one CTE2 ppm/°C 75 75 74 75 75 72 76 75 74 76 76 Glass transition temperature (Tg) ℃ 145 145 155 150 150 165 140 155 150 145 160 Bending strength @rt N/ ^mm2 125 122 133 120 125 115 128 137 123 133 122 Flexural modulus of elasticity @rt N/ ^mm2 20000 18500 21000 18500 19000 21000 19000 21000 19000 19000 22000 Bending strength @260 N/ ^mm2 6 6 8 8 7 13 6 7 8 8 15 Flexural modulus of elasticity @260 N/ ^mm2 230 210 230 220 210 500 230 240 230 220 600

As can be seen from the results in Table 2, according to the thermosetting resin composition of the second invention, a dielectric substrate with excellent high dielectric constant and low dielectric loss tangent can be obtained, in other words, a dielectric substrate with excellent balance of these characteristics. body substrate. Furthermore, it was found that the thermosetting resin composition of the present invention has a long flow length of the spiral flow and has excellent moldability because the gel time is within an appropriate range.

This application claim is based on Japanese Patent Application No. 2021-051748 filed on March 25, 2021, Japanese Patent Application No. 2021-172197 filed on October 21, 2021, and Japanese Patent Application No. 2021 filed on December 6, 2021 2021-197667, Japanese Patent Application No. 2021-197669 filed on December 6, 2021, Japanese Patent Application No. 2021-197679 filed on December 6, 2021, Japanese Patent Application filed on December 6, 2021 I wish to claim the priority of Japanese Application No. 2021-197731 filed on December 6, 2021 and Japanese Application No. 2021-197720, and use all the contents disclosed therein.

10:Microstrip antenna 12: Dielectric substrate 14: Radiation conductor board 16: Grounding conductor plate 20,20': microstrip antenna 22: Dielectric substrate 24: High dielectric substrate 26: spacer a: Gap

[FIG. 1] It is a top perspective view which shows the microstrip antenna of this embodiment. [ Fig. 2 ] is a cross-sectional view showing another aspect of the microstrip antenna of this embodiment.

10:Microstrip antenna

12: Dielectric substrate

14: Radiation conductor board

16: Grounding conductor plate

h: thickness

L: Length

W: width

Claims (24)

A thermosetting resin composition, which contains: a thermosetting resin; a high dielectric constant filler, with a specific permittivity of 10 or more at 25°C and 25 GHz; and an active ester compound, which will be measured in the following order, When the flexural modulus at 25°C is set to FM ₂₅ , and the flexural modulus at 260°C is set to FM ₂₆₀ , FM ₂₅ and FM ₂₆₀ satisfy 0.005≤FM ₂₆₀ /FM ₂₅ ≤0.1, (sequence) Use low-pressure injection The molding machine injects and molds the thermosetting resin composition into the mold under the conditions that the mold temperature is 130° C., the injection pressure is 9.8 MPa, and the curing time is 300 seconds, thereby obtaining a mold with a width of 10 mm, a thickness of 4 mm, and a length of 80mm molded product, post-harden the obtained molded product at 175°C for 4 hours, prepare a test piece, and measure the flexural modulus of the test piece at room temperature (25°C) or 260°C according to JIS K 6911 (N/mm ² ). The thermosetting resin composition according to claim 1, wherein, when the flexural strength at 25°C is set to FS ₂₅ and the flexural strength at 260°C is set to FS ₂₆₀ according to JIS K 6911 in the aforementioned order, FS ₂₅ and FS ₂₆₀ satisfy 0.025≤FS ₂₆₀ /FS ₂₅ ≤0.2. The thermosetting resin composition according to claim 1 or 2, wherein, The glass transition temperature of the cured product of the thermosetting resin composition is not less than 100°C and not more than 250°C. The thermosetting resin composition according to claim 1 or 2, wherein, In the cured product of the aforementioned thermosetting resin composition, the linear expansion coefficient CTE1 in the range below the glass transition temperature is 5 ppm/°C to 25 ppm/°C, and the linear expansion coefficient CTE2 in the range exceeding the glass transition temperature and 320°C or below is Above 30ppm/°C and below 100ppm/°C. The thermosetting resin composition according to claim 1 or 2, wherein, The aforementioned high dielectric constant filler contains calcium titanate. The thermosetting resin composition according to claim 1 or 2, wherein, The content of the high dielectric constant filler is not less than 30% by mass and not more than 90% by mass in 100% by mass of the thermosetting resin composition. The thermosetting resin composition according to claim 1 or 2, wherein, The aforementioned active ester compounds include: active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolac, phenol novolak containing phenol At least one of active ester compounds of formyl compounds. The thermosetting resin composition according to claim 1 or 2, wherein the aforementioned active ester compound has a structure represented by the following general formula (1),

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

In the general formula (B), Ar is a substituted or unsubstituted arylene group, Y is a single bond, a substituted or unsubstituted straight-chain alkylene group with 1 to 6 carbons, or a substituted or unsubstituted A substituted cyclic alkylene group with 3 to 6 carbons, a substituted or unsubstituted divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group or a pyloxy group, n is An integer of 0 to 4, k is the average value of the repeating unit, and is in the range of 0.25 to 3.5. The thermosetting resin composition according to claim 1 or 2, wherein, The aforementioned thermosetting resin includes: an epoxy resin containing a biphenylene skeleton. The thermosetting resin composition according to claim 1 or 2, which further contains a phenolic curing agent. The thermosetting resin composition according to claim 10, wherein, The aforementioned phenolic curing agent includes: a phenolic resin containing a biphenylene skeleton. The thermosetting resin composition according to claim 1 or 2, 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 thermosetting resin composition comprising: (A) epoxy resin; (B) hardeners; and (C) a high dielectric constant filler, and The epoxy resin (A) contains biphenyl aralkyl type epoxy resin and/or biphenyl type epoxy resin (excluding biphenyl aralkyl type epoxy resin), Hardener (B) contains active ester hardener and phenolic hardener, The high dielectric constant filler (C) contains: calcium titanate, barium titanate, strontium titanate, magnesium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, zirconium At least one of barium titanate, calcium zirconate titanate, lead zirconate titanate, barium magnesium niobate and calcium zirconate, The high dielectric constant filler (C) is contained 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 thermosetting resin composition according to claim 14 or 15, wherein, The aforementioned active ester hardener is selected from active ester hardeners containing a dicyclopentadiene-type diphenol structure, active ester hardeners containing a naphthalene structure, and active ester hardeners containing acetylated phenol novolaks. and at least one active ester-based hardener containing benzoyl compounds of phenol novolac. The thermosetting resin composition according to claim 14 or 15, wherein the active ester-based hardener has a structure represented by the following general formula (1),

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

In the general formula (B), Ar is a substituted or unsubstituted arylene group, Y is a single bond, a substituted or unsubstituted straight-chain alkylene group with 1 to 6 carbons, or a substituted or unsubstituted Substituted cyclic alkylene group with 3 to 6 carbons, substituted or unsubstituted divalent aromatic hydrocarbon group, ether bond, carbonyl, carbonyloxy, sulfide group or pyloxy group, n is 0 to 4 Integer, k is the average value of repeating units, and is in the range of 0.25-3.5. The thermosetting resin composition according to claim 14 or 15, further comprising a curing catalyst (D). The thermosetting resin composition according to claim 14 or 15, which is used as a material for forming a microstrip antenna. The thermosetting resin composition according to claim 14 or 15, which is used as a material for forming a dielectric waveguide. The thermosetting resin composition according to claim 14 or 15, 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 microstrip antenna, which has: The dielectric substrate of claim 22; a radiation conductor plate disposed on one side of the aforementioned dielectric substrate; and The ground conductor plate is provided on the other surface of the dielectric substrate. A microstrip antenna, which has: Dielectric substrate; a radiation conductor plate disposed on one side of the aforementioned dielectric substrate; a grounding conductor plate disposed on the other side of the aforementioned dielectric substrate; and a high dielectric body disposed opposite to the aforementioned radiating conductor plate, and The above-mentioned high dielectric body is composed of the dielectric substrate of claim 22.

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