CN117120504A - Thermosetting resin composition, high-frequency device, dielectric substrate, and microstrip antenna - Google Patents

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

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Publication number
CN117120504A
CN117120504A CN202280024604.2A CN202280024604A CN117120504A CN 117120504 A CN117120504 A CN 117120504A CN 202280024604 A CN202280024604 A CN 202280024604A CN 117120504 A CN117120504 A CN 117120504A
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China
Prior art keywords
thermosetting resin
resin composition
group
active ester
titanate
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Chinese (zh)
Inventor
木村俊次
田中刚志
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority claimed from PCT/JP2022/013057 external-priority patent/WO2022202781A1/en
Publication of CN117120504A publication Critical patent/CN117120504A/en
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Abstract

The thermosetting resin composition of the present invention comprises: a thermosetting resin; a high dielectric constant filler having a relative dielectric constant of 10 or more at 25 ℃ and 25 GHz; and an active ester compound, the flexural modulus at 25 ℃ being FM 25 And the flexural modulus at 260℃was set to FM 260 FM when 25 And FM 260 Meet FM of 0.005 ∈or less 260 /FM 25 Less than or equal to 0.1. The thermosetting resin composition of the present invention comprises: (A) an epoxy resin; (B) a curing agent; and (C) a high dielectric constant filler. The epoxy resin (a) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin (except for the biphenyl aralkyl type epoxy resin). The curing agent (B) contains an active ester curing agent and a phenol curing agent. The high dielectric constant filler (C) contains at least 1 selected from the group consisting of calcium titanate, barium titanate, strontium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium titanate, lead titanate zirconate, barium magnesium niobate, and calcium zirconate, and the high dielectric constant filler (C) is contained in an amount of 30 mass% or more in 100 mass% of the thermosetting resin composition.

Description

Thermosetting resin composition, high-frequency device, dielectric substrate, and microstrip antenna
Technical Field
The invention relates to a thermosetting resin composition, a high-frequency device, a dielectric substrate, and a microstrip antenna.
Background
In recent years, wireless communication has been accelerated, and further, high performance and miniaturization have been demanded for communication devices used. In recent years, the capacity of wireless communication has rapidly increased, and the bandwidth and the frequency of the use of transmission signals have been increased rapidly. Therefore, the use frequency band of the communication device cannot be handled only by the microwave frequency band that has been used in the past, and is expanding to the millimeter wave frequency band. In view of such a background, an antenna mounted in a communication device is strongly required to have high performance.
In the communication device, when the dielectric constant of the antenna material (dielectric substrate) assembled inside the communication device becomes high, further miniaturization can be achieved. When the dielectric loss tangent of the dielectric substrate is reduced, the loss is reduced, which is advantageous for higher frequencies. Therefore, if a dielectric substrate having a high dielectric constant and a small dielectric loss tangent can be used, it is possible to achieve higher frequencies and further to achieve reduction in circuit size and miniaturization of communication equipment.
Patent document 1 discloses an antenna having a circuit board, which is a laminate of a dielectric board that is a composite material including a fluororesin and a glass cloth and an antenna having a two-dimensional roughness Ra of less than 0.2 μm on a surface in contact with the fluororesin. This document describes a dielectric constant and a dielectric loss tangent of a circuit board measured at 1 GHz.
Patent document 2 discloses a resin composition comprising a siloxane-modified polyamideimide resin, a high dielectric constant filler, and an epoxy resin, wherein the cured product has a relative dielectric constant of 15 or more under the conditions of 25 ℃ and 1 MHz. Examples of the use of 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 curing agent. This document describes that the resin composition can be used as a high dielectric constant insulating material for electronic components used in a high frequency region and a high dielectric constant insulating material for fingerprint sensors. Examples of the use of barium titanate as the dielectric powder are described in the examples of this document.
Patent document 4 discloses a molding resin composition for sealing an electronic component in a high-frequency device, which contains an epoxy resin, a curing agent, and an inorganic filler containing calcium titanate particles and strontium titanate particles in a prescribed amount, the inorganic filler further containing at least one selected from silica particles and alumina particles.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2018-41998
Patent document 2: japanese patent laid-open No. 2004-315653
Patent document 3: japanese patent laid-open No. 2020-105523
Patent document 4: japanese patent No. 6870778
Disclosure of Invention
Technical problem to be solved by the invention
However, the conventional techniques described in patent documents 1 to 4 have room for improvement in the following aspects.
The present inventors have found that the composite material described in patent document 1 has room for improvement in terms of high dielectric constant and low dielectric loss tangent in a higher frequency band and in terms of durability at heat. As a first technical problem.
The dielectric substrates described in patent documents 1 to 4 have technical problems in terms of high dielectric constant and low dielectric loss tangent, and the technical problems are remarkable particularly in the high frequency band. As a second technical problem.
Means for solving the technical problems
The present inventors have found that the above-mentioned first technical problem can be solved by using a high dielectric constant filler and an active ester compound together in a thermosetting resin composition and controlling the ratio of flexural modulus at 260 ℃ to flexural modulus at 25 ℃ within an appropriate range, thereby completing the first invention.
That is, the first invention can be expressed as follows.
According to a first aspect of the present invention, there is provided a thermosetting resin composition comprising:
a thermosetting resin;
a high dielectric constant filler having a relative dielectric constant of 10 or more at 25 ℃ and 25 GHz; and
an active ester compound is provided which is a compound of,
the flexural modulus at 25℃measured according to the following procedure was set as FM 25 And the flexural modulus at 260℃was set to FM 260 FM when 25 And FM 260 Meet FM of 0.005 ∈or less 260 /FM 25 ≤0.1。
(flow path)
The thermosetting resin composition was injection molded in a mold at a mold temperature of 130℃under an injection pressure of 9.8MPa for a curing time of 300 seconds using a low-pressure transfer molding machine to obtain a molded article having a width of 10mm, a thickness of 4mm and a length of 80 mm.
The obtained molded article was post-cured at 175℃for 4 hours to prepare a test piece.
The flexural modulus of the test piece was measured at room temperature, namely 25℃or 260℃in N/mm in accordance with JIS K6911 2 。
Further, according to the first invention, there is provided a high-frequency device comprising the cured product of the thermosetting resin composition described above.
The present inventors have found that the above-described second technical problem can be solved by combining specific components, and completed a second invention.
That is, the second invention can be expressed as follows.
According to a second aspect of the present invention, there is provided a thermosetting resin composition comprising:
(A) An epoxy resin;
(B) A curing agent; and
(C) A filler with a high dielectric constant,
the epoxy resin (a) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin (other than the biphenyl aralkyl type epoxy resin),
the curing agent (B) contains an active ester curing agent and a phenol curing agent,
the high dielectric constant filler (C) contains at least 1 selected from the group consisting of calcium titanate, barium titanate, strontium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium titanate, lead titanate zirconate, barium magnesium niobate, and calcium zirconate, and the high dielectric constant filler (C) is contained in an amount of 30 mass% or more in 100 mass% of the thermosetting resin composition.
According to a second aspect of the present invention, there is provided a dielectric substrate obtained by curing the thermosetting resin composition.
According to the first or second aspect of the present invention, there is provided a microstrip antenna comprising:
the dielectric substrate;
a radiation conductor plate provided on one surface of the dielectric substrate; and
And a ground conductor plate provided on the other surface of the dielectric substrate.
According to the first or second aspect of the present invention, there is provided a microstrip antenna comprising:
a dielectric substrate;
a radiation conductor plate provided on one surface of the dielectric substrate;
a ground conductor plate provided on the other surface of the dielectric substrate; and
a high dielectric disposed opposite the radiation conductor plate,
the high dielectric is constituted by the dielectric substrate.
Effects of the invention
According to the first invention, a thermosetting resin composition capable of forming a member excellent in high dielectric constant, low dielectric loss tangent and durability at heat, and a high-frequency device using the thermosetting resin composition can be provided.
Further, according to the second invention, a thermosetting resin composition which can provide a dielectric substrate having a high dielectric constant and a low dielectric loss tangent and is excellent in moldability, a dielectric substrate comprising the resin composition, and a microstrip antenna comprising the dielectric substrate can be provided. In other words, the thermosetting resin composition of the second invention can provide a dielectric substrate having an excellent balance between a high dielectric constant and a low dielectric loss tangent.
Drawings
Fig. 1 is a top perspective view showing a microstrip antenna according to the present embodiment.
Fig. 2 is a cross-sectional view showing another embodiment of the microstrip antenna according to the present embodiment.
Detailed Description
Hereinafter, according to embodiment 1, the first invention (claims 1 to 13 and 22 to 24 at the time of application) will be described with reference to the accompanying drawings, and according to embodiment 2, the second invention (claims 14 to 21 and 22 to 24 at the time of application) will be described with reference to the accompanying drawings.
In all the drawings, the same components are denoted by the same reference numerals, and description thereof is omitted as appropriate. For example, "1 to 10" means "1 or more" to "10 or less" unless otherwise specified.
[ first invention ]
An outline of the thermosetting resin composition of embodiment 1 will be described.
The thermosetting resin composition of the present embodiment comprises: a thermosetting resin; a high dielectric constant filler having a relative dielectric constant of 10 or more at 25 ℃ and 25 GHz; and an active ester compound, the flexural modulus at 25℃measured according to the following procedure is set as FM 25 And the flexural modulus at 260℃was set to FM 260 FM when 25 And FM 260 Meet FM of 0.005 ∈or less 260 /FM 25 ≤0.1。
FM 260 /FM 25 The lower limit of (2) is 0.005 or more, preferably 0.006 or more, more preferably 0.007 or more, and even more preferably 0.008 or more. Thus, in a member (cured product of the thermosetting resin composition) having a high dielectric constant and a low dielectric loss tangent, durability at heat can be improved.
FM, on the other hand 260 /FM 25 The upper limit of (2) may be, 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. This can balance the physical properties of the cured product of the thermosetting resin composition.
Currently, the temperature of the operating environment is increasing due to design conditions such as high frequency, high output of power semiconductors, and low height of devices. In order to cope with such a high temperature of the working environment, the inventors have studied on thermal characteristics of a cured product of a thermosetting resin composition.
According to the findings of the present inventors, the FM described above 260 /FM 25 The degree of deformation of the cured product of the thermosetting resin composition before and after heat treatment can be evaluated stably. The inventors of the present invention have found that FM is used as an index 260 /FM 2s Above the lower limit, thermal degradation of the cured product due to heating can be suppressed, and therefore the thermal durability of the component formed using the cured product can be improved.
In addition, in the above-described member, it is also expected to suppress a decrease in dielectric characteristics due to thermal degradation.
In this embodiment, for example, the FM can be controlled by appropriately selecting the types and amounts of the components contained in the thermosetting resin composition, the method for producing the thermosetting resin composition, and the like 260 /FM 25 The following FS 260 /FS 25 Glass transition temperature and linear expansion coefficient. Among these, as a method for making the FM described above 260 /FM 25 The following FS 260 /FS 25 Examples of the elements having a glass transition temperature and a linear expansion coefficient within a desired range of values include calcium titanate as a high dielectric constant filler, a high dielectric constant filler content, aluminum oxide as an inorganic filler, a biphenyl type epoxy resin and/or a phenol aralkyl type epoxy resin containing a biphenylene skeleton as a thermosetting resin, and an active ester compound containing a dicyclopentadiene type diphenol structure as an active ester compound, and a biphenyl aralkyl type resin and/or a phenol aralkyl type resin containing a biphenylene skeleton as a phenol curing agent.
The thermosetting resin composition may be formed such that the bending strength at 25℃measured at a head speed of 5mm/min according to JIS K6911 according to the above-mentioned procedure is FS 25 And the bending strength at 260℃was set to FS 260 At the time FS 25 And FS 260 Meet the FS of 0.025 ∈ 260 /FS 25 ≤0.2。
FS 260 /FS 25 The lower limit of (2) is 0.025 or more, preferably 0.028 or more, more preferably 0.030 or more, and still more preferably 0.032 or more. Thus, in a member (cured product of the thermosetting resin composition) having a high dielectric constant and a low dielectric loss tangent, the toughness at heat can be improved.
On the other hand, FS 260 /FS 25 The upper limit of (2) 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. This can balance the physical properties of the cured product of the thermosetting resin composition.
(flow of measurement of flexural modulus and flexural Strength)
The thermosetting resin composition was injection molded in a mold at a mold temperature of 130℃under an injection pressure of 9.8MPa and a curing time of 300 seconds using a low-pressure transfer molding machine, to obtain a molded article having a width of 10mm, a thickness of 4mm and a length of 80 mm.
The obtained molded article was post-cured at 175℃for 4 hours to prepare a test piece,
the flexural modulus of elasticity (N/mm) of the test piece was measured at room temperature (25 ℃) and 260℃respectively at a head speed of 5mm/min in accordance with JIS K6911 2 ) And flexural Strength (N/mm) 2 )。
The lower limit of the glass transition temperature of the cured product of the thermosetting resin composition is, for example, 100℃or higher, preferably 103℃or higher, and more preferably 105℃or higher.
The upper limit of the glass transition temperature of the cured product is not particularly limited, but may be, for example, 250℃or lower.
The coefficient of linear expansion of the cured product of the thermosetting resin composition in the range of not more than the glass transition temperature is CTE1, and the coefficient of linear expansion in the range of not more than 320 ℃ exceeding the glass transition temperature is CTE2.
CTE1 is, for example, 5 ppm/DEG C or more and 25 ppm/DEG C or less, preferably 5 ppm/DEG C or more and 23 ppm/DEG C or less.
CTE2 is, for example, 30 ppm/DEG C or more and 100 ppm/DEG C or less, preferably 30 ppm/DEG C or more and 90 ppm/DEG C or less.
The components of the thermosetting resin composition of the present embodiment will be described in detail below.
[ thermosetting resin ]
The thermosetting resin composition of the present 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 these, epoxy resins can be used.
The epoxy resin can be any of monomers, oligomers, and polymers having 2 or more epoxy groups in 1 molecule, and the molecular weight and molecular structure thereof are not limited.
Examples of the epoxy resin include biphenyl type epoxy resins; bisphenol type epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, and tetramethyl bisphenol F type epoxy resin; stilbene type epoxy resins; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; a multifunctional epoxy resin such as a triphenol methane type epoxy resin, an alkyl modified triphenol methane type epoxy resin, or the like; phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene skeleton, naphthol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having a biphenylene skeleton, and naphthol aralkyl type epoxy resins having a biphenylene skeleton; an epoxy resin comprising a biphenylene backbone; a dihydroxynaphthalene type epoxy resin, a naphthol type epoxy resin such as an epoxy resin obtained by subjecting a dihydroxynaphthalene dimer to glycidol etherification; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene modified phenolic epoxy resin and other bridged cyclic hydrocarbon compound modified phenolic epoxy resin. These may be used alone or in combination of 2 or more.
Among these, the epoxy resin containing a biphenylene skeleton is preferable, and 1 or more selected from the group consisting of a biphenylaralkyl type epoxy resin and a biphenylene type epoxy resin (excluding the biphenylaralkyl type epoxy resin) is more preferable.
The content of the thermosetting resin in 100 mass% of the thermosetting resin composition is, for example, 2 mass% or more, preferably 5 mass% or more, and more preferably 7 mass% or more.
The content of the epoxy resin may be, for example, 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less, based on 100 mass% of the thermosetting resin composition.
[ high dielectric constant filler ]
The thermosetting resin composition of the present embodiment contains a high dielectric constant filler (high dielectric constant filler).
Examples of the high dielectric constant filler include calcium titanate, strontium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium titanate, lead titanate zirconate, barium magnesium niobate, calcium zirconate, and the like, and 1 or 2 or more kinds selected from them can be used.
Regarding the high dielectric constant filler, in the above examples, at least one of calcium titanate and strontium titanate may be contained, preferably calcium titanate is contained. This can further reduce the dielectric loss tangent in the high frequency band.
The average particle diameter of the high dielectric constant filler is, for example, preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 20 μm, still more preferably 0.5 μm to 10 μm.
The high dielectric constant filler is in the form of particles, amorphous, flakes, or the like, and the high dielectric constant filler of these shapes can be used in any ratio.
The content of the high dielectric constant filler is preferably in the range of 30 to 90 mass%, more preferably in the range of 35 to 80 mass%, and even more preferably in the range of 40 to 70 mass% in 100 mass% of the thermosetting resin composition. When the amount of the high dielectric constant filler added is within the above range, the dielectric constant of the obtained cured product becomes lower, and the production of molded articles is also excellent.
[ active ester Compound ]
The thermosetting resin composition of the present embodiment contains an active ester compound (active ester curing agent).
The active ester compound functions as a curing agent for thermosetting resins such as epoxy resins.
As the active ester compound, a compound having 1 or more active ester groups in 1 molecule can be used. Among them, preferred are compounds having 2 or more reactive ester groups in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds.
Preferable specific examples of the active ester compound include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylate of phenol novolac, and active ester compounds containing a benzoyl of phenol novolac. The active ester compounds can comprise at least 1 selected from them.
Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. "dicyclopentadiene type diphenol structure" means a 2-valent structural unit composed of phenylene dicyclopentylene-phenylene.
In this embodiment, for example, a resin having a structure represented by the following general formula (1) is used as the active ester compound.
In formula (1), "B" is a structure represented by formula (B).
In formula (B), ar is a substituted or unsubstituted arylene group. Examples of the substituent of the substituted arylene group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group, and the like.
Y is a single bond, a substituted or unsubstituted straight-chain alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 2 valences, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group or a sulfone group. Examples of the substituent of the above-mentioned group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group and the like.
Y is preferably a single bond, methylene, -CH (CH) 3 ) 2 -ether bond, cycloalkylene group which may be substituted, 9-fluorenylene group which may be substituted, etc.
n is an integer of 0 to 4, preferably 0 or 1.
Specifically, B is a structure represented by the following general formula (B1) or the following general formula (B2).
In the above general formula (B1) and the above general formula (B2), ar and Y have the same meanings as those of the general formula (B).
A is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group,
ar' is a substituted or unsubstituted aryl group,
k is an average value of repeating units and is in the range of 0.25 to 3.5.
The thermosetting resin composition of the present embodiment can provide a cured product having excellent dielectric characteristics and excellent dielectric loss tangent, by containing a specific active ester compound.
The active ester compound used in the thermosetting resin composition of the present embodiment has an active ester group represented by formula (B). In the curing 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 groups are blocked by the ester residues 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 1 selected from the following formulas (B-1) to (B-6).
In the formulae (B-1) to (B-6),
R 1 each independently represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group,
R 2 each independently represents any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, X represents any one of a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group,
n is an integer of 0 to 4, and p is an integer of 1 to 4.
Since the structures represented by the above formulae (B-1) to (B-6) are all highly oriented, the cured product of the obtained thermosetting resin composition can have a low dielectric loss tangent in a high frequency band when the active ester compound containing the same is used.
Among them, from the viewpoint of low dielectric loss tangent, an active ester compound having a structure represented by the formula (B-2), the formula (B-3) or the formula (B-5) is preferable, and an active ester compound further having a structure in which n of the formula (B-2) is 0, a structure in which X of the formula (B-3) is an ether bond, or a structure in which two carbonyloxy groups are located at 4,4' -positions in the formula (B-5) is more preferable. And R in the formulae is preferably 1 All hydrogen atoms.
The term "Ar'" in the formula (1) is an aryl group, and may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 3, 5-xylyl, o-biphenyl, m-biphenyl, p-biphenyl, 2-benzyl phenyl, 4- (. Alpha. -cumyl) phenyl, 1-naphthyl, 2-naphthyl, or the like. Among them, 1-naphthyl group or 2-naphthyl group is particularly preferable from the viewpoint of obtaining a cured product having a low dielectric loss tangent.
In this embodiment, the [ a ] in the active ester compound represented by the formula (1) is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group, and examples of such arylene group include a structure obtained by addition polymerization of an unsaturated aliphatic cyclic hydrocarbon compound having 2 double bonds in 1 molecule and a phenolic compound.
Examples of the unsaturated aliphatic cyclic hydrocarbon compound having 2 double bonds in 1 molecule include dicyclopentadiene, a polymer of cyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene, and limonene, and these may be used alone or in combination of 2 or more. Among these, dicyclopentadiene is preferable from the viewpoint of obtaining a cured product excellent in heat resistance. Further, dicyclopentadiene is contained in a petroleum fraction, and therefore, polymers of cyclopentadiene, other aliphatic or aromatic diene compounds, and the like may be contained in industrial dicyclopentadiene as impurities, but when properties such as heat resistance, curability, moldability, and the like are considered, a product having a dicyclopentadiene purity of 90 mass% or more is preferably used.
On the other hand, examples of the phenolic compound include phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1, 4-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, and 2, 7-dihydroxynaphthalene, and these may be used singly or in combination of 2 or more. Among these, phenol is preferable from the viewpoint of being an active ester compound having high curability and excellent dielectric characteristics 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). A cured product of a thermosetting resin composition containing an active ester compound having the following structure as [ A ] in the formula (1) can realize a low dielectric loss tangent in a high frequency band.
In the formula (A), the amino acid sequence of the formula (A),
R 3 each independently represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group,
l is 0 or 1, and m is an integer of 1 or more.
More preferable resins among the active ester compounds represented by the formula (1) include resins represented by the following formulas (1-1), (1-2) and (1-3), and particularly preferable resins include resins represented by the following formulas (1-3).
In the formula (1-1), R 1 And R is 3 Each independently represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group, Z represents a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l represents 0 or 1, and k represents an average value of repeating units of 0.25 to 3.5.
In the formula (1-2), R 1 And R is 3 Each independently represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group, Z represents a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l represents 0 or 1, and k represents an average value of repeating units of 0.25 to 3.5.
In the formula (1-3), R 1 And R is 3 Each independently represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group, Z represents a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, 1 represents 0 or 1, and k represents an average value of repeating units of 0.25 to 3.5.
The active ester compound represented by the above general formula (a) can be produced by a known method in which a phenolic compound (a) having a structure in which a plurality of aryl groups having phenolic hydroxyl groups are formed via aliphatic cyclic hydrocarbon-based nodules, an aromatic nucleus-containing dicarboxylic acid or a halide thereof (b), and an aromatic monohydroxy compound (c) are reacted.
The reaction ratio of the phenolic compound (a), the aromatic nucleus-containing dicarboxylic acid or the halide (b) thereof and the aromatic monohydroxy compound (c) can be appropriately adjusted according to the desired molecular design, but from the viewpoint of obtaining an active ester compound having higher curability, it is preferable to use each raw material in a ratio of 0.25 to 0.90 mole of phenolic hydroxyl group in the phenolic compound (a) and 0.10 to 0.75 mole of hydroxyl group in the aromatic monohydroxy compound (c) and 0.50 to 0.75 mole of hydroxyl group in the aromatic monohydroxy compound (c) relative to 1 mole of the total of carboxyl groups or acid halide groups in the aromatic nucleus-containing dicarboxylic acid or the halide (b) thereof.
In addition, when the total of the arylcarbonyloxy groups and the phenolic hydroxyl groups in the resin structure is the number of functional groups of the resin, the functional group equivalent of the active ester compound is preferably in the range of 200g/eq to 230g/eq, more preferably in the range of 210g/eq to 220g/eq, from the viewpoint that a cured product excellent in curability and low in dielectric loss tangent can be obtained.
In the thermosetting resin composition of the present embodiment, the contents of the active ester compound and the epoxy resin are preferably in the following proportions from the viewpoint of obtaining a cured product excellent in curability and low in dielectric loss tangent: the epoxy groups in the epoxy resin are 0.8 to 1.2 equivalents relative to 1 equivalent of the total of the active groups in the active ester compound. The active group in the active ester compound means an arylcarbonyloxy group and a phenolic hydroxyl group which are present in the resin structure.
In 100% by mass of the thermosetting resin composition, the active ester compound is preferably used in an amount of 0.5% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 12% by mass or less, and still more preferably 2% by mass or more and 9% by mass or less.
By containing the specific active ester compound in the above range, the obtained cured product can have more excellent dielectric characteristics, and further excellent low dielectric loss tangent.
The thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent even in a high frequency band by using the active ester compound in combination with the high dielectric constant filler.
From the viewpoint of the above effects, the active ester compound may contain: the amount of the high dielectric constant filler is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 3 to 15 parts by mass, based on 100 parts by mass of the high dielectric constant filler.
[ curing agent ]
The thermosetting resin composition of the present embodiment can contain a curing agent other than the active ester compound.
As the other curing agent, a phenol curing agent, an amine compound curing agent, an amide compound curing agent, an acid anhydride curing agent, and the like can be used. These may be used alone or in combination of 2 or more. Among them, a phenolic curing agent can be used.
Examples of the phenolic curing agent include polyhydric phenol compounds such as phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenolic resins, dicyclopentadiene phenol addition resins, phenolic resins containing biphenylene skeletons, phenol aralkyl resins, naphthol aralkyl resins, trimethylol methane resins, tetraphenol ethane resins, naphthol novolac resins, naphthol-phenol copoly novolac resins, naphthol-cresol copoly novolac resins, biphenyl modified phenol novolac resins (polyhydric phenol compounds in which phenol cores are linked by a bisphenol), biphenyl modified naphthol novolac resins (polyhydric naphthalene phenol compounds in which phenol cores are linked by a bisphenol), aminotriazine modified phenolic resins (polyhydric phenol compounds in which phenol cores are linked by a melamine or benzomelamine).
Among them, biphenyl aralkyl type phenol resins can be used.
Examples of the amine compound curing agent include diaminodiphenylmethane (DDM), diethylenetriamine (DETA), triethylenetetramine (TETA), diaminodiphenylsulfone, isophoronediamine, imidazole and BF 3 Amine compounds such as amine complexes and guanidine derivatives.
The amide compound-based curing agent includes, for example, a polyamide resin synthesized from dicyandiamide, a dimer of linoleic acid and ethylenediamine.
Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride (PMDA), maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
When the curing agent is used, the amount of the curing agent to be blended is preferably 0.5 mass% to 15 mass%, more preferably 1 mass% to 10 mass%, based on 100 mass% of the thermosetting resin. By using the curing agent in the amount within the above range, a thermosetting resin composition having excellent curability can be obtained.
[ curing catalyst ]
The thermosetting resin composition may contain a curing catalyst.
The curing catalyst is sometimes also referred to as a curing accelerator or the like. The curing catalyst is not particularly limited as long as it can accelerate the curing reaction of the thermosetting resin, and a known curing catalyst can be used.
Specifically, phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds with quinone compounds, and adducts of phosphonium compounds with silane compounds; imidazoles (imidazole-based curing accelerators) such as 2-methylimidazole and 2-phenylimidazole; examples of the nitrogen atom-containing compound include amidines such as 1, 8-diazabicyclo [5.4.0] undecene-7 and benzyldimethylamine, and nitrogen atom-containing compounds such as tertiary amines and quaternary salts of amidines and amines, and only 1 kind of nitrogen atom-containing compound may be used, or 2 kinds or more of nitrogen atom-containing compounds may be used.
Among these, from the viewpoint of improving curability and obtaining a magnetic material excellent in mechanical strength such as flexural strength, a compound containing a phosphorus atom is preferable, and a compound having a latent property such as a tetrasubstituted phosphonium compound, a phosphate betaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound is more preferable, and a tetrasubstituted phosphonium compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound are particularly preferable.
By using the compound (C) represented by the general formula (1) in combination with a latent curing catalyst, a magnetic material having more excellent moldability and more excellent mechanical strength such as bending strength can be obtained.
Examples of the organic phosphine include primary phosphines such as ethyl phosphine and phenyl phosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine and the like.
In the case of using the curing catalyst, the content thereof is preferably 0.05 to 3% by mass, more preferably 0.08 to 2% by mass, in 100% by mass of the thermosetting resin composition. When the content of the curing catalyst is within such a numerical range, the curing acceleration effect can be sufficiently obtained without excessively deteriorating other properties.
[ inorganic filler ]
The thermosetting resin composition of the present embodiment can contain an inorganic filler in addition to the high dielectric constant filler to reduce hygroscopicity, reduce linear expansion coefficient, improve thermal conductivity, and improve strength.
Examples of the inorganic filler include powders of fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, magnesium silicate, steatite, spinel, mullite, titanium dioxide, and the like, and beads and glass fibers obtained by spheroidizing these powders. These inorganic fillers may be used alone or in combination of 2 or more. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoints of fluidity at the time of molding and mold abrasion.
The content of the inorganic filler other than the high dielectric constant filler may be preferably in the range of 3 mass% to 60 mass% in 100 mass% of the thermosetting resin composition, more preferably in the range of 5 mass% to 50 mass% from the viewpoints of moldability, reduction in thermal expansion and improvement in strength. When the amount is within the above range, the thermal expansion property and moldability are reduced and excellent.
[ other Components ]
The thermosetting resin composition of the present embodiment may contain various components such as a silane coupling agent, a release agent, a colorant, a dispersant, and a stress reducing agent, as required, in addition to the above components.
In particular, examples of the silane coupling agent include an amino group-containing silane coupling agent and a mercapto group-containing silane coupling agent. In addition, from the viewpoint of uniformly mixing the high dielectric constant filler with the inorganic filler, the miscibility of the high dielectric constant filler with an organic component such as an epoxy resin, and the flexural strength/flexural modulus, it is preferable to use 2 or more kinds of these.
[ thermosetting resin composition ]
The thermosetting resin composition of the present embodiment can be produced by uniformly mixing the above components. As a manufacturing method, the following method can be mentioned: the raw materials of a predetermined content are sufficiently mixed by a mixer or the like, and then melt-kneaded by a mixing roll, kneader, extruder or the like, and then cooled and pulverized. The thermosetting resin composition thus obtained can be briquetted, if necessary, in a size and quality conforming to molding conditions.
Since the cured product obtained from the thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent in a high frequency band, it is possible to achieve high frequency and further to achieve shortening of circuits and miniaturization of high frequency equipment such as communication equipment.
Such a thermosetting resin composition can be used to form a part of a high-frequency device selected from a microstrip antenna, a dielectric waveguide, and a multilayer antenna.
The high-frequency device of the present embodiment includes a cured product obtained from the thermosetting resin composition.
An example of the high-frequency device will be described below.
< microstrip antenna >
As shown in fig. 1, the microstrip antenna 10 includes a dielectric substrate 12 obtained by curing the thermosetting resin composition, a radiation conductor plate (radiation element) 14 provided on one surface of the dielectric substrate 12, and a ground conductor plate 16 provided on the other surface of the dielectric substrate 12.
The shape of the radiation conductor plate may be rectangular or circular. In the present embodiment, an example of using the rectangular radiation conductor plate 14 will be described.
The radiation conductor plate 14 includes any one of a metal material, an alloy of the metal material, a cured product of a metal paste, and a conductive polymer. The metal material contains copper, silver, palladium, gold, platinum, aluminum, chromium, nickel, cadmium, lead, selenium, manganese, tin, vanadium, lithium, cobalt, titanium, and the like. The alloy comprises a plurality of metallic materials. The metal paste contains a powder of a metal material mixed with an organic solvent and a binder. The adhesive comprises epoxy resin, polyester resin, polyimide resin, polyamide imide resin, polyether imide resin. The conductive polymer includes polythiophene-based polymer, polyacetylene-based polymer, polyaniline-based polymer, polypyrrole-based polymer, and the like.
As shown in fig. 1, the microstrip antenna 10 of the present embodiment has a radiation conductor plate 14 having a length L and a width W, and resonates at a frequency at which L coincides with an integer multiple of 1/2 wavelength. As in the present embodiment, when the dielectric substrate 12 having a high dielectric constant is used, the thickness h of the dielectric substrate 12 and the width W of the radiation conductor plate 14 are designed to be sufficiently small with respect to the wavelength.
The ground conductor plate 16 is a thin plate made of a metal having high conductivity such as copper, silver, or gold. The thickness of the antenna device may be sufficiently small relative to the center operating frequency of the antenna device, and may be about 1 wavelength of 50 minutes to about 1 wavelength of 1000 minutes of the center operating frequency.
Examples of the feeding method of the microstrip antenna include a direct feeding method such as a coaxial feeding (back feeding) and a coplanar feeding, and an electromagnetic coupling (electromagnetically coupled) feeding method such as a slot-coupled feeding and a proximity-coupled (proximity coupled) feeding.
The coaxial feed (back feed) can feed the radiating conductor plate 14 from the back of the antenna using a coaxial line or connector passing through the ground conductor plate 16 and the dielectric substrate 12.
The coplanar feed can feed the radiation conductor plate 14 through a microstrip line (not shown) disposed on the same side as the radiation conductor plate 14.
In the slot-coupled feed, another dielectric substrate (not shown) is further provided in the form of an interposed ground conductor plate 16, and the radiation conductor plate 14 and the microstrip line are formed on different dielectric substrates. The radiation conductor plate 14 is electromagnetically coupled to the microstrip line through a gap formed in the ground conductor plate 16, thereby exciting the radiation conductor plate 14.
In the proximity coupling feed, the dielectric substrate 12 has a laminated structure in which a dielectric substrate formed with the radiation conductor plate 14 and a dielectric substrate provided with the strip conductor of the microstrip line and the ground conductor plate 16 are laminated. The radiation conductor plate 14 is excited by electromagnetically coupling the radiation conductor plate 14 with the microstrip line by extending the strip conductor of the microstrip line to the lower portion of the radiation conductor plate 14.
Fig. 2 (a) and 2 (b) show another microstrip antenna system. The same reference numerals are given to the same components as those in fig. 1, and the description thereof is omitted appropriately.
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, 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 separated by a predetermined distance through the spacer 26.
The dielectric substrate 22 is made of a low dielectric constant substrate such as a polytetrafluoroethylene substrate.
The high dielectric substrate 24 is composed of a dielectric substrate obtained by curing the resin composition.
The space between the dielectric substrate 22 and the high dielectric substrate 24 may be a space or may be filled with a dielectric material.
As shown in the microstrip antenna 20' of fig. 2 (b), the high dielectric substrate 24 may be brought into contact with the upper surface of the radiation conductor plate 14.
< dielectric waveguide >
In this embodiment, the dielectric waveguide includes a dielectric formed by curing the thermosetting resin composition of this embodiment and a conductor film covering the surface of the dielectric. The dielectric waveguide encloses electromagnetic waves in a dielectric medium (dielectric medium) for transmission.
The conductor film may be made of a metal such as copper, an oxide high-temperature superconductor, or the like.
< multilayer antenna >
In this embodiment, the multilayer antenna includes a dielectric sheet obtained by curing the thermosetting resin composition of this embodiment.
Specifically, the multilayer antenna is a modular device in which a circuit including a plurality of elements such as a capacitor and an inductor is printed on a dielectric sheet and laminated.
[ second invention ]
The thermosetting resin composition according to embodiment 2 contains an epoxy resin (a), a curing agent (B) and a high dielectric constant filler (C), and the high dielectric constant filler (C) is contained in an amount of 30 mass% or more based on 100 mass% of the composition.
[ 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 (other than the biphenyl aralkyl type epoxy resin).
The biphenyl aralkyl type epoxy resin of the present embodiment preferably has a structural unit represented by the following general formula (a).
In the general formula (a), the amino acid sequence of the formula (a),
ra and Rb, where plural are present, are each independently a 1-valent organic group, a hydroxyl group, or a halogen atom,
r and s are each independently 0 to 4,
* Indicating bonding to other radicals.
Specific examples of the 1-valent organic group of Ra and Rb include alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkylaryl, cycloalkyl, alkoxy, heterocyclic, carboxyl, and the like.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
Examples of the alkynyl group include an ethynyl group and the like.
Examples of the alkylene group include methylene and ethylene.
Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl and anthracenyl.
Examples of the aralkyl group include benzyl and phenethyl.
Examples of the alkylaryl group include tolyl and xylyl.
Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, and n-hexoxy.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
R a And R is b The total number of carbon atoms of the 1-valent organic groups of (2) is, for example, 1 to 30, preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6, respectively.
r and s are each independently preferably 0 to 2, more preferably 0 to 1. Alternatively, r and s are both 0.
R c Where a plurality is present, each independently is a 1-valent organic group, a hydroxyl group, or a halogen atom,
t is an integer of 0 to 3.
As R c Specific examples of the 1-valent organic group include R a And R is b The same examples as those specifically mentioned.
t is preferably 0 to 2, more preferably 0 to 1.
The weight average molecular weight Mw of the biphenyl aralkyl type epoxy resin of the present embodiment is preferably 500 to 2000, more preferably 600 to 1900, and even more preferably 700 to 1800.
The dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the biphenyl aralkyl type epoxy resin is preferably 2.0 to 4.0, more preferably 1.8 to 3.8, and still more preferably 1.6 to 3.6. The dispersibility is preferably adjusted to make the physical properties of the epoxy resin uniform.
The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) are calculated, for example, using polystyrene equivalent values obtained from a calibration curve of standard Polystyrene (PS) obtained by GPC measurement. The measurement conditions of GPC measurement are, for example, as follows.
Gel permeation chromatography device HLC-8320GPC manufactured by Tosoh Co., ltd (TOSOH CORPORATION)
And (3) pipe column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Co., ltd
A detector: RI detector for liquid chromatograms
Measuring temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Sample concentration: 2.0 mg/ml
The biphenyl type epoxy resin of the present embodiment can be represented by the following general formula (b).
In the general formula (b), R's each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
Specific examples of the biphenyl type epoxy resin include diglycidyl ether of 4,4' -dihydroxybiphenyl, diglycidyl ether of 3,3', 5' -tetramethyl-4, 4' -dihydroxybiphenyl, diglycidyl ether of 3,3', 5' -tetra-t-butyl-4, 4' -dihydroxybiphenyl, diglycidyl ether of dimethyl dipropyl diphenol, diglycidyl ether of dimethyl diphenol, and the like.
The epoxy resin (a) may contain other epoxy resins in addition to the above 2 epoxy resins within a range that does not impair the effects of the present invention.
Examples of the other epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and glycidylamine type epoxy resin.
In the present embodiment, the content of the "biphenyl aralkyl type epoxy resin and/or biphenyl type epoxy resin" in the epoxy resin (a) is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, still more preferably 80% by mass or more and 100% by mass or less, and the epoxy resin (a) may contain only these 2 epoxy resins.
From the viewpoint of the effect of the present invention, the thermosetting resin composition (100 mass%) of the present embodiment may contain the epoxy resin (a) in an amount of preferably 2 mass% to 30 mass%, more preferably 3 mass% to 25 mass%, and still more preferably 5 mass% to 20 mass%.
[ curing agent (B) ]
In the present embodiment, the curing agent (B) includes an active ester curing agent and a phenol curing agent. By combining these curing agents, a thermosetting resin composition which can obtain a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent and is excellent in moldability can be obtained.
(active ester-based curing agent)
As the active ester-based curing agent, the same compounds as those described in the embodiment of the first invention can be used, and can be produced in the same manner.
When the active ester-based curing agent is a resin having a structure represented by the general formula (1), it is preferable that "B" in the general formula (1) is a structure represented by the formulae (B-1) to (B-6). Since the structures represented by the above formulas (B-1) to (B-6) are all highly oriented, when an active ester-based curing agent comprising the above structure is used, the cured product of the obtained thermosetting resin composition has a low dielectric loss tangent and excellent adhesion to metals, and therefore can be suitably used as a semiconductor sealing material.
In addition, when the total of the arylcarbonyloxy groups and the phenolic hydroxyl groups in the resin structure is the number of functional groups of the resin, the functional group equivalent of the active ester-based curing agent is preferably in the range of 200g/eq to 230g/eq, more preferably in the range of 210g/eq to 220g/eq, from the viewpoint of obtaining a cured product excellent in curability and low in dielectric loss tangent.
In the thermosetting resin composition of the present embodiment, the blending amount of the active ester-based curing agent and the epoxy resin is preferably the following ratio from the viewpoint of obtaining a cured product excellent in curability and low in dielectric loss tangent: the epoxy groups in the epoxy resin are 0.8 to 1.2 equivalents relative to 1 equivalent of the total active groups in the active ester-based curing agent. The active group in the active ester-based curing agent means an arylcarbonyloxy group and a phenolic hydroxyl group in the resin structure.
In the composition of the present embodiment, the active ester-based curing agent is preferably used in an amount of 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and still more preferably 1.0% by mass or more and 7% by mass or less, relative to the entire thermosetting resin composition.
By including the specific active ester-based curing agent in the above range, the obtained cured product can have more excellent dielectric characteristics, and further excellent low dielectric loss tangent.
The resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent even in a high frequency band by using the active ester-based curing agent in combination with a high dielectric constant filler described later.
From the viewpoint of the above effects, the active ester-based curing agent may include: the amount of the high dielectric constant filler is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 3 to 15 parts by mass, based on 100 parts by mass of the high dielectric constant filler to be described later.
Further, as described in Japanese patent application laid-open No. 2020-90615, the present inventors have developed a resin composition comprising an epoxy resin and a predetermined active ester-based curing agent for use in sealing semiconductors, which is different from the present application. The present application is different from the technique described in Japanese patent application laid-open No. 2020-90615 in that a filler having a high dielectric constant is contained. Further, since the filler having a high dielectric constant is contained, the effect obtained by the combination of the active ester-based curing agent and the epoxy resin is different in terms of having a high dielectric constant and being excellent in terms of high dielectric constant and low dielectric loss tangent in a high frequency band.
(phenolic curing agent)
Examples of the phenolic curing agent include polyhydric phenol compounds such as phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenolic resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylol methane resins, tetraphenol ethane resins, naphthol novolac resins, naphthol-phenol copoly novolac resins, naphthol-cresol copoly novolac resins, biphenyl modified phenol novolac resins (polyhydric phenol compounds in which phenol cores are linked by a dimethylene), biphenyl modified naphthol novolac resins (polyhydric naphthalene phenol compounds in which phenol cores are linked by a dimethylene), and aminotriazine modified phenolic resins (polyhydric phenol compounds in which phenol cores are linked by a melamine or benzomelamine).
The amount of the phenolic curing agent blended is preferably 20 mass% or more and 70 mass% or less with respect to the epoxy resin (a). By using the curing agent in the amount within the above range, a resin composition having excellent curability can be obtained.
The content ratio (b (parts by mass)/a (parts by mass)) of the phenolic curing agent b to the active ester curing agent a may be preferably 0.5 to 8, more preferably 1 to 5, still more preferably 1.5 to 3.
By containing the active ester-based curing agent and the phenol-based curing agent in the above ratio, the obtained cured product can have more excellent dielectric characteristics, and further, the low dielectric loss tangent is more excellent.
In the composition of the present embodiment, the curing agent (B) including the active ester curing agent and the phenol curing agent is preferably used in an amount of 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and still more preferably 1.0% by mass or more and 7% by mass or less, relative to the entire thermosetting resin composition.
By including the specific active ester-based curing agent in the above range, the obtained cured product can have more excellent dielectric characteristics, and further excellent low dielectric loss tangent.
[ high dielectric constant filler (C) ]
In the present embodiment, as the high dielectric constant filler (C), calcium titanate, barium titanate, strontium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium titanate, lead titanate, barium magnesium niobate, calcium zirconate, and the like can be cited, and at least 1 selected from them can be contained. By containing these high dielectric constant fillers, a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent can be obtained.
From the viewpoint of the effect of the present invention, the filler having a high dielectric constant is preferably at least 1 selected from the group consisting of calcium titanate, strontium titanate and magnesium titanate, and more preferably at least 1 selected from the group consisting of calcium titanate and magnesium titanate.
The high dielectric constant filler is in the form of particles, amorphous, flakes, or the like, and the high dielectric constant filler in any ratio can be used. The average particle diameter of the high dielectric constant filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 20 μm, still more preferably 0.5 μm to 10 μm, from the viewpoint of the effect of the present invention and the viewpoint of fluidity/filling property.
The amount of the high dielectric filler to be blended is in the range of 30 mass% or more, preferably in the range of 35 mass% or more, more preferably in the range of 45 mass% or more, based on 100 mass% of the thermosetting resin composition. The upper limit is about 80 mass% or less.
When the addition amount of the high dielectric constant filler is within the above range, the dielectric constant of the obtained cured product becomes lower, and the production of molded articles is also excellent.
[ curing catalyst (D) ]
The thermosetting resin composition of the present embodiment may further contain a curing catalyst (D).
The curing catalyst (D) is sometimes also referred to as a curing accelerator or the like. The curing catalyst (D) is not particularly limited as long as it can accelerate the curing reaction of the thermosetting resin, and a known curing catalyst can be used.
Specific examples of the curing catalyst (D) include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphoric acid ester betaine compounds, adducts of phosphine compounds with quinone compounds, and adducts of phosphonium compounds with silane compounds; imidazoles (imidazole-based curing accelerators) such as 2-methylimidazole and 2-phenylimidazole; examples of the nitrogen atom-containing compound include amidines such as 1, 8-diazabicyclo [5.4.0] undecene-7 and benzyldimethylamine, and nitrogen atom-containing compounds such as tertiary amines and quaternary salts of amidines and amines, and only 1 kind of nitrogen atom-containing compound may be used, or 2 kinds or more of nitrogen atom-containing compounds may be used.
Among these, from the viewpoint of improving curability and obtaining a magnetic material excellent in mechanical strength such as flexural strength, a compound containing a phosphorus atom is preferable, and a compound having a latent property such as a tetrasubstituted phosphonium compound, a phosphate betaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound is more preferable, and a tetrasubstituted phosphonium compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound are particularly preferable.
By using the epoxy resin (a) containing a naphthol aralkyl type epoxy resin in combination with a latent curing catalyst, a magnetic material having more excellent moldability and more excellent mechanical strength such as bending strength can be obtained.
Examples of the organic phosphine include primary phosphines such as ethyl phosphine and phenyl phosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine and the like.
Examples of the tetra-substituted phosphonium compound include a compound represented by the following general formula (6).
In the general formula (6), the amino acid sequence,
p represents a phosphorus atom.
R 4 、R 5 、R 6 And R is 7 Each independently represents an aromatic group or an alkyl group.
A represents an anion of an aromatic organic acid having at least 1 functional group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring.
AH represents an aromatic organic acid having at least 1 functional group selected from a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring.
x and y are 1 to 3, z is 0 to 3, and x=y.
The compound represented by the general formula (6) is obtained, for example, in the following manner.
First, a tetra-substituted phosphonium halide, an aromatic organic acid, and a base are added to an organic solvent and uniformly mixed, and an aromatic organic acid anion is generated inside the solution system. Then, when water is added, the compound represented by the general formula (6) can be precipitated. Among the compounds represented by the general formula (6), R bonded to a phosphorus atom is preferable 4 、R 5 、R 6 And R is 7 A compound in which phenyl group is used and AH has a hydroxyl group in an aromatic ring, namely, a phenol, and a is an anion of the phenol. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcinol, catechol, and the like; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene and anthracenediol; bisphenols such as bisphenol a, bisphenol F, bisphenol S, etc.; and polycyclic phenols such as phenylphenol and biphenol.
Examples of the phosphate betaine compound include a compound represented by the following general formula (7).
In the general formula (7),
p represents a phosphorus atom.
R 8 Represents an alkyl group having 1 to 3 carbon atoms, R 9 Represents a hydroxyl group.
f is 0 to 5, g is 0 to 3.
The compound represented by the general formula (7) is obtained, for example, in the following manner.
First, the tertiary phosphine is obtained by a step of bringing a tertiary aromatic substituted phosphine into contact with a diazonium salt to replace the diazonium group of the tertiary aromatic substituted phosphine and the diazonium salt.
Examples of the adduct of the phosphine compound and the quinone compound include a compound represented by the following general formula (8).
In the general formula (8),
p represents a phosphorus atom.
R 10 、R 11 And R is 12 The alkyl group having 1 to 12 carbon atoms or the aryl group having 6 to 12 carbon atoms may be the same or different from each other.
R 13 、R 14 And R is 15 Represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, which may be the same as or different from each other, R 14 And R is R 15 Can be bonded into a ring structure.
The phosphine compound used for the adduct of the phosphine compound and the quinone compound is preferably, for example, a phosphine compound in which a substituent such as an alkyl group or an alkoxy group is not substituted in an aromatic ring, such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthalene phosphine, or tris (benzyl) phosphine, and examples of the substituent such as an alkyl group or an alkoxy group include substituents having a carbon number of 1 to 6. Triphenylphosphine is preferred from the viewpoint of easy availability.
Further, as the quinone compound used for the adduct of the phosphine compound and the quinone compound, benzoquinone and anthraquinones are exemplified, 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, an adduct can be obtained by bringing into contact and mixing them in a solvent capable of dissolving both an organic tertiary phosphine and a benzoquinone. Among ketones such as acetone and methyl ethyl ketone, ketones having low solubility in adducts are preferred as the solvent. However, the present invention is not limited thereto.
R bonded to phosphorus atom in the compound represented by the general formula (8) 10 、R 11 And R is 12 Is phenyl, and R 13 、R 14 And R is 15 Is hydrogen sourceThe compound obtained by adding 1, 4-benzoquinone to triphenylphosphine is preferable in terms of lowering the thermal elastic modulus of the cured product of the sealing resin composition.
Examples of the adduct of the phosphonium compound and the silane compound include a compound represented by the following general formula (9).
In the general formula (9), the amino acid sequence of the compound,
p represents a phosphorus atom, and Si represents a silicon atom.
R 16 、R 17 、R 18 And R is 19 The organic group or the aliphatic group each having an aromatic ring or a heterocyclic ring may be the same as or different from each other.
R 20 Is a group Y 2 And Y 3 A bonded organic group.
R 21 Is a group Y 4 And Y 5 A bonded organic group.
Y 2 And Y 3 A group Y representing a proton-donating group releasing a proton and a group in the same molecule 2 And Y 3 Bonded to silicon atoms to form a chelate structure.
Y 4 And Y 5 A group Y representing a proton-donating group releasing a proton and a group in the same molecule 4 And Y 5 Bonded to silicon atoms to form a chelate structure.
R 20 And R is 21 May be the same as or different from each other, Y 2 、Y 3 、Y 4 And Y 5 May be the same as or different from each other.
Z 1 Is an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring.
In the general formula (9), R is 16 、R 17 、R 18 And R is 19 Examples thereof include phenyl, methylphenyl, methoxyphenyl, and the like,Among these, an aromatic group or an unsubstituted aromatic group having a substituent such as an alkyl group, an alkoxy group, or a hydroxyl group, such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, or a hydroxynaphthyl group, is more preferable.
In the general formula (9), R 20 Is Y with 2 And Y 3 A bonded organic group. Similarly, R 21 Is with the group Y 4 And Y 5 A bonded organic group. Y is Y 2 And Y 3 A group which is a proton-donating group and which releases a proton, and a group Y in the same molecule 2 And Y 3 Bonded to silicon atoms to form a chelate structure. Similarly, Y 4 And Y 5 A group which is a proton-donating group and which releases a proton, and a group Y in the same molecule 4 And Y 5 Bonded to silicon atoms to form a chelate structure. Group R 20 And R is 21 May be the same as or different from each other, a group Y 2 、Y 3 、Y 4 And Y 5 May be the same as or different from each other. The general formula (9) is represented by-Y 2 -R 20 -Y 3 -and Y 4 -R 21 -Y 5 The group represented by (a) is a group formed by releasing 2 protons from a proton donor, and as the proton donor, an organic acid having at least 2 carboxyl groups or hydroxyl groups in the molecule is preferable, an aromatic compound having at least 2 carboxyl groups or hydroxyl groups at the adjacent carbon constituting the aromatic ring is more preferable, an aromatic compound having at least 2 hydroxyl groups at the adjacent carbon constituting the aromatic ring is more preferable, and catechol, pyrogallol, 1, 2-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2 '-biphenol, 1' -bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranic acid, tannic acid, 2-hydroxybenzyl alcohol, 1, 2-cyclohexanediol, 1, 2-propanediol, glycerol and the like are more preferable, but catechol, 1, 2-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene and the like are more preferable.
Z in the general formula (9) 1 Represents an organic or aliphatic radical having an aromatic or heterocyclic ringSpecific examples of the group include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl and octyl, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, reactive substituents such as glycidoxypropyl, mercaptopropyl, aminopropyl and the like having glycidoxy, mercapto, alkyl having amino, vinyl and the like, but among these, methyl, ethyl, phenyl, naphthyl and biphenyl are more preferable in terms of heat stability.
The method for producing the adduct of the phosphonium compound and the silane compound is, for example, as follows.
A silane compound such as phenyltrimethoxysilane and a proton donor such as 2, 3-dihydroxynaphthalene were added to a flask containing methanol and dissolved therein, and then a sodium methoxide-methanol solution was added dropwise thereto while stirring at room temperature. Then, when a solution prepared in advance in which a tetra-substituted phosphonium halide such as tetraphenyl phosphonium bromide is dissolved in methanol is added dropwise thereto with stirring at room temperature, crystals are precipitated. When the precipitated crystals are filtered, washed with water and dried in vacuum, an adduct of the phosphonium compound and the silane compound can be obtained.
In the case of using the curing catalyst (D), the content thereof is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass, relative to 100% by mass of the thermosetting resin composition. When the content of the curing catalyst (D) is within such a numerical range, the curing acceleration effect can be sufficiently obtained without excessively deteriorating other properties.
[ inorganic filler ]
The thermosetting resin composition of the present embodiment may contain an inorganic filler in addition to the high dielectric constant filler (C) to reduce hygroscopicity, reduce linear expansion coefficient, improve thermal conductivity and improve strength.
Examples of the inorganic filler include powders of fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, magnesium silicate, steatite, spinel, mullite, titanium dioxide, and the like, and beads and glass fibers obtained by spheroidizing these. These inorganic fillers may be used alone or in combination of 2 or more. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoints of fluidity at the time of molding and mold abrasion.
The amount of the inorganic filler other than the high dielectric constant filler (C) to be added may be preferably in the range of 10 mass% to 50 mass%, more preferably in the range of 15 mass% to 40 mass%, and even more preferably in the range of 20 mass% to 35 mass%, relative to 100 mass% of the thermosetting resin composition, from the viewpoints of moldability, reduction in thermal expansibility, and improvement in strength. When the amount is within the above range, the thermal expansion property and moldability are reduced and excellent.
[ other Components ]
The thermosetting resin composition of the present embodiment may contain various components such as a silane coupling agent, a release agent, a colorant, a dispersant, and a stress reducing agent, as required, in addition to the above components.
The thermosetting resin composition of the present embodiment contains the following epoxy resin (a), the following curing agent (B), and the following high dielectric constant filler (C), and the high dielectric constant filler (C) is contained in an amount of 30 mass% or more in 100 mass% of the composition.
Epoxy resin (a): comprising a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin.
Curing agent (B): comprises an active ester-based curing agent and a phenol-based curing agent.
High dielectric constant filler (C): comprises at least 1 selected from calcium titanate, barium titanate, strontium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium titanate zirconate, lead titanate zirconate, barium magnesium niobate and calcium zirconate.
According to the thermosetting resin composition of the present embodiment, which is obtained by combining such components, a dielectric substrate having a high dielectric constant and a low dielectric loss tangent can be obtained, and further, a microstrip antenna including the dielectric substrate can be provided.
The thermosetting resin composition of the present embodiment may contain the epoxy resin (a) in an amount of preferably 2 to 30 mass%, more preferably 3 to 25 mass%, still more preferably 5 to 20 mass% based on 100 mass% of the composition,
the curing agent (B) may be contained in an amount of preferably 0.2 to 15 mass%, more preferably 0.5 to 10 mass%, still more preferably 1.0 to 7 mass% based on 100 mass% of the composition,
the high dielectric constant filler (C) may be contained in an amount of 30 mass% or more, preferably 35 mass% or more, more preferably 45 mass% or more, based on 100 mass% of the composition. The upper limit is 80 mass%.
In the present embodiment, a thermosetting resin composition which can provide a dielectric substrate having a high dielectric constant and a low dielectric loss tangent can be provided by combining an epoxy resin (a), a curing agent (B), and a high dielectric constant filler (C), and by containing 30 mass% or more of the high dielectric constant filler (C) in 100 mass% of the composition.
The thermosetting resin composition of the present embodiment can be produced by uniformly mixing the above components. As a manufacturing method, the following method can be mentioned: the raw materials of a predetermined blending amount are sufficiently mixed by a mixer or the like, and then melt-kneaded by a mixing roll, kneader, extruder or the like, and then cooled and pulverized. The thermosetting resin composition thus obtained can be briquetted, if necessary, in a size and quality conforming to molding conditions.
The thermosetting resin composition of the present embodiment has a spiral flow length of 70cm or more, preferably 80cm or more, more preferably 90cm or more, and still more preferably 100cm or more. Therefore, the thermosetting resin composition of the present embodiment is excellent in moldability.
The spiral flow test can be performed, for example, by: resin molding material was injected into a spiral flow measuring mold according to EMMI-1-66 using a low pressure transfer molding machine (KTS-15 manufactured by Shang Jiuji Co., ltd. (KOHTAKI Corporation)) under the conditions of a mold temperature of 175 ℃, an injection pressure of 6.9MPa, and a curing time of 120 seconds, and the flow length was measured.
The gel time of the thermosetting resin composition of the present embodiment is preferably 32 seconds to 80 seconds, more preferably 35 seconds to 70 seconds.
When the gel time of the thermosetting resin composition is not less than the above-mentioned lower limit, the filling property is excellent, and when the gel time of the thermosetting resin composition is not more than the above-mentioned upper limit, the moldability is improved.
The thermosetting resin composition of the present embodiment has a rectangular pressure of 0.1MPa or more, preferably 0.15MPa or more, and more preferably 0.20MPa or more, measured under the following conditions.
Rectangular pressure is a parameter of melt viscosity, and the smaller the value, the lower the melt viscosity. The thermosetting resin composition of the present embodiment is excellent in mold filling property at the time of molding by rectangular pressure within the above range.
(conditions)
Using a low pressure transfer molding machine, at a mold temperature of 175℃and an injection speed of 177mm 3 Under the condition of/second, a thermosetting resin composition was injected into a rectangular flow path having a width of 13mm, a thickness of 1mm and a length of 175mm, and the pressure change with time was measured by a pressure sensor embedded at a position 25mm from the upstream front end of the flow path, and the lowest pressure at the time of flowing the thermosetting resin composition was calculated 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 ℃ for 90 minutes and curing the composition.
The dielectric constant of 25GHz obtained by the cavity resonance method may be 10 or more, preferably 12 or more, and more preferably 13 or more.
The dielectric loss tangent (tan δ) of 25GHz obtained by the cavity resonance method may be 0.04 or less, preferably 0.03 or less, more preferably 0.02 or less, and particularly preferably 0.015 or less.
Since the cured product obtained from the thermosetting resin composition of the present embodiment is excellent in high dielectric constant and low dielectric loss tangent in a high frequency band, it is possible to achieve high frequency and further reduction in circuit size and miniaturization of communication equipment and the like, and it is possible to suitably use the cured product as a material for forming a microstrip antenna, a material for forming a dielectric waveguide, a material for forming an electromagnetic wave absorber and the like.
< microstrip antenna >
As in the first embodiment of the present invention, the microstrip antenna of the present embodiment has the structure shown in fig. 1, fig. 2 (a), and fig. 2 (b), and therefore, the description thereof is omitted.
< dielectric waveguide >
In this embodiment, the dielectric waveguide includes a dielectric formed by curing the thermosetting resin composition of this embodiment and a conductor film covering the surface of the dielectric. The dielectric waveguide encloses electromagnetic waves in a dielectric medium (dielectric medium) for transmission.
The conductor film may be made of a metal such as copper, an oxide high-temperature superconductor, or the like.
< electromagnetic wave absorber >
In this embodiment, the electromagnetic wave absorber includes a structure in which a support, a resistive film, a dielectric layer, and a reflective layer are laminated. The electromagnetic wave absorber can be used as a lambda/4 type electromagnetic wave absorber having high electromagnetic wave absorption performance.
The support may be a resin base material or the like. The support can protect the resistive film, and can improve durability as a radio wave absorber.
The resistive film may be a resistive film containing indium tin oxide or molybdenum.
The dielectric layer is formed by curing the thermosetting resin composition of the present embodiment. The thickness is about 10 μm to 2000 μm.
The reflective layer may function as a reflective layer for electric waves, and examples thereof include a metal film.
While the embodiments of the present invention have been described above, these are examples of the present invention, various aspects other than the above may be employed within a range that does not impair the effects of the present invention.
Examples (example)
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Examples of the invention 1 (claims 1 to 13, 22 to 24) and embodiment 1 are shown in example a.
Examples according to invention 2 (claims 14 to 21, 22 to 24 at the time of application) and embodiment 2 are shown as example B.
Example A ]
Examples A1 to A4 and comparative example A1
< preparation of thermosetting resin composition >
The following raw materials were mixed at the contents shown in table 1 using a mixer at normal temperature, and then roll kneaded at 70 to 100 ℃. Then, the obtained kneaded material was cooled and then pulverized to obtain a thermosetting resin composition in the form of powder. Next, ingot molding is performed under high pressure to obtain an ingot-shaped thermosetting resin composition.
The information of the raw materials in table 1 is shown below.
(high dielectric constant filler)
High dielectric constant filler 1: calcium titanate (CT, average particle diameter of 2.0 μm, fuji titanium Co., ltd. (Fuji Titanium Industry Co., ltd.) and relative permittivity at 25 ℃ C., 1 GHz: 135)
(inorganic filler)
Inorganic filler 1: alumina (K75-1V 25F, manufactured by electric Co., ltd. (Denka Company Limited))
Inorganic filler 2: fused spherical silica (SC-2500-SQ, manufactured by Kagaku Kogyo Dou Ma (Admatechs Company Limited))
(thermosetting resin)
Epoxy resin 1: biphenyl type epoxy resin (YX 4000K, mitsubishi chemical Co., ltd. (Mitsubishi Chemical Corporation))
Epoxy resin 2: phenol aralkyl type epoxy resin having biphenylene skeleton (NC 3000L, manufactured by Nippon Kayaku co., ltd.)
Epoxy resin 3: bisphenol A type epoxy resin (YL 6810, mitsubishi chemical Co., ltd.)
(active ester Compound)
Active ester compound 1: active ester compound prepared by the following preparation method
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 279.1g (mole number of acid chloride groups: 2.0 mole) of biphenyl-4, 4' -dicarboxylic acid dichloride and 1338g of toluene, and the inside of the system was purged with nitrogen under reduced pressure to dissolve the same. Then, 96.5g (0.67 mol) of α -naphthol and 219.5g (molar number of phenolic hydroxyl groups: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the inside of the system was dissolved by nitrogen substitution under reduced pressure. Thereafter, 400g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while keeping the temperature inside the system at 60℃or lower while purging with nitrogen. Then, stirring was continued under this condition for 1.0 hour. After the completion of the reaction, the mixture was allowed to stand for separation, and the aqueous layer was removed. Then, water was added to the toluene phase in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was left to stand for separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, the water was removed by dewatering with a decanter to obtain an active ester resin in the form of a toluene solution having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, the resin had R in the above formula (1-1) 1 And R is 3 Is a hydrogen atom, Z is a naphthyl group, and l is a structure of 0. The average value k of the repeating units is in the range of 0.5 to 1.0 based on the result of calculation of the reaction equivalent ratio.
Active ester compound 2: active ester compound prepared by the following preparation method
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 203.0g of 1, 3-benzenedicarboxylic acid dichloride (mole number of acid chloride groups: 2.0 mol) and 1338g of toluene, and the inside of the system was reducedThe mixture was dissolved by nitrogen substitution. Then, 96.5g (0.67 mol) of α -naphthol and 219.5g (molar number of phenolic hydroxyl groups: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the inside of the system was dissolved by nitrogen substitution under reduced pressure. Thereafter, 400g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while keeping the temperature inside the system at 60℃or lower while purging with nitrogen. Then, stirring was continued under this condition for 1.0 hour. After the completion of the reaction, the mixture was allowed to stand for separation, and the aqueous layer was removed. Then, water was added to the toluene phase in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was left to stand for separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, the water was removed by dewatering with a decanter to obtain an active ester resin in the form of a toluene solution having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, the resin had R in the above formula (1-3) 1 And R is 3 Is a hydrogen atom, Z is a naphthyl group, and 1 is 0. 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 of calculation of the reaction equivalent ratio. Specifically, the obtained active ester resin has a structure represented by the following chemical formula. In the following formula, the average value k of the repeating units is 0.5 to 1.0.
(curing agent)
Phenolic curing agent 1: biphenyl aralkyl resin (HE 910-20, manufactured by AIR WATER INC)
Phenolic curing agent 2: phenol aralkyl resin having biphenylene skeleton (MEH-7851 SS, manufactured by Ming He Chemie Co., ltd. (MEIWA PLASTIC INDUSTRIES, LTD.))
(silane coupling agent)
Silane coupling agent 1: phenylaminopropyl trimethoxysilane (CF 4083, tolydakanin Co., ltd.)
Silane coupling agent 2: 3-mercaptopropyl trimethoxysilane (Sila-Ace, manufactured by JNC Corporation)
(curing catalyst)
Curing catalyst 1: tetraphenylphosphonium-4, 4' -sulfonyldiphenol salt
Curing catalyst 2: tetraphenylphosphonium bis (naphthalene-2, 3-dioxy) phenylsilicate
(Release agent)
Mold release agent 1: trimontanyl glyceride (Licolab WE-4, manufactured by Clariant Japan K.K.), kaolin Co., ltd.
(evaluation of dielectric constant and dielectric loss tangent by Cavity resonance method)
The obtained thermosetting resin composition was applied to a Si substrate, and prebaked at 120℃for 4 minutes to form a resin film having a coating film thickness of 12. Mu.m.
This was heated under nitrogen atmosphere for 90 minutes at 200℃using an oven, and subjected to hydrofluoric acid treatment (immersed in a 2 mass% aqueous hydrofluoric acid solution). After the substrate was taken out of the hydrofluoric acid, the cured film was peeled off from the Si substrate, and this was used as a test piece.
The measuring device was manufactured using Network Analyzer HP8510C, synthesized sweeper HP83651A, and test set HP8517B (each manufactured by agilent technologies (japan) limited (Agilent Technologies Japan, ltd.). These devices and cylindrical cavity resonators (having an inner diameter of phi 42mm and a height of 30 mm) were mounted.
In a state where the test piece was inserted into the above resonator and in a non-inserted state, the resonance frequency, 3dB bandwidth, penetration power ratio, and the like were measured at a frequency of 18 GHz. Then, these measurement results were analytically calculated by software, and dielectric characteristics of dielectric constant (Dk) and dielectric loss tangent (Df) were obtained. In addition, the measurement mode is set to TE 011 A mode.
(glass transition temperature, coefficient of linear expansion)
The glass transition temperature (Tg) and the coefficients of linear expansion (CTE 1, CTE 2) of the cured product of the obtained thermosetting resin composition were measured in the following manner. First, a thermosetting resin composition for sealing was injection molded using a low pressure transfer molding machine (KTS-15 manufactured by Shang Jim Co., ltd.) at a mold temperature of 175℃under an injection pressure of 6.9MPa and a curing time of 120 seconds, to obtain test pieces of 10mm X4 mm. Subsequently, the obtained test piece was post-cured at 175℃for 4 hours, and then measured using a thermo-mechanical analyzer (TMA 100 manufactured by Seiko electronic industries, inc. (Seiko Instruments & Electronics Ltd.) at a temperature ranging from 0℃to 320℃and a temperature rising rate of 5℃per minute). From the measurement results, a glass transition temperature (Tg), a coefficient of linear expansion (CTE 1) lower than the glass transition temperature, and a coefficient of linear expansion (CTE 2) higher than the glass transition temperature were calculated.
(evaluation of mechanical Strength (flexural Strength, flexural modulus of elasticity))
The obtained thermosetting resin composition was injection molded in a mold using a low pressure transfer molding machine ("KTS-30" manufactured by Shang Jim Co., ltd.) under the conditions of a mold temperature of 130 ℃, an injection pressure of 9.8MPa and a curing time of 300 seconds. Thus, a molded article having a width of 10mm, a thickness of 4mm and a length of 80mm was obtained. Subsequently, the obtained molded article was post-cured at 175℃for 4 hours. Thus, test pieces for evaluating mechanical strength were produced. Thereafter, the bending strength (N/mm) of the test piece at room temperature (25 ℃) or 260℃was measured at a head speed of 5mm/min in accordance with JIS K6911 2 ) And flexural modulus of elasticity (N/mm) 2 )。
(durability at Hot)
The rate of change in physical properties of the cured product of the obtained thermosetting resin composition after 10 times of repeated application of the heat history at 175℃for 100 hours was evaluated. When the flexural modulus at 260℃before the heat history before the repeated application was set to FMa and the flexural modulus at 260℃before the heat history after the repeated application was set to FMb, the change rate obtained from (FMa-FMb)/FMa X100% was evaluated as "O" when the change rate was within 200%, and as "X" when the change rate was over 200%.
The thermosetting resin compositions of examples A1 to A4 according to the first invention showed the results of being able to form a part (cured product) excellent in high dielectric constant and low dielectric loss tangent in a high frequency band and in durability when compared with comparative example A1.
Such a thermosetting resin composition can be suitably used for forming a part of a high-frequency device such as a microstrip antenna, a dielectric waveguide, and a multilayer antenna.
< example B >
Examples B1 to B10 and comparative example B1
The following raw materials were mixed in the mixing amounts shown in table 2 at normal temperature using a mixer, and then roll kneaded at 70 to 100 ℃. Then, the obtained kneaded material was cooled and then pulverized to obtain a particulate resin composition. Next, ingot molding is performed under high pressure to obtain an ingot-shaped resin composition.
(high dielectric constant filler)
High dielectric constant filler 1: calcium titanate (average particle size of 2.0 μm)
(inorganic filler)
Inorganic filler 1: alumina (DAB 25MA-TS3, manufactured by electric Co., ltd.)
Inorganic filler 2: fused spherical silica (SC-2500-SQ manufactured by Kagaku Kogyo Dou Ma)
(colorant)
Colorant 1: black titanium oxide (AKO KASEI co., ltd.)
(coupling agent)
Coupling agent 1: phenylaminopropyl trimethoxysilane (CF-4083, manufactured by Toli Corning Co., ltd.)
Coupling agent 2: 3-mercaptopropyl-trimethoxysilane (Sila-Ace, manufactured by JNC Co., ltd.)
(epoxy resin)
Epoxy resin 1: phenol aralkyl type epoxy resin containing biphenylene skeleton (manufactured by Nippon Kayaku Co., ltd., NC-3000L, containing a structural unit represented by the above general formula (a))
(curing agent)
Curing agent 1: active ester-based curing agent prepared by the following preparation method
(Process for producing active ester-based curing agent)
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 279.1g (mole number of acid chloride groups: 2.0 mole) of biphenyl-4, 4' -dicarboxylic acid dichloride and 1338g of toluene, and the inside of the system was purged with nitrogen under reduced pressure to dissolve the same. Then, 96.5g (0.67 mol) of α -naphthol and 219.5g (molar number of phenolic hydroxyl groups: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the inside of the system was dissolved by nitrogen substitution under reduced pressure. Thereafter, 400g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while keeping the temperature inside the system at 60℃or lower while purging with nitrogen. Then, stirring was continued under this condition for 1.0 hour. After the completion of the reaction, the mixture was allowed to stand for separation, and the aqueous layer was removed. Then, water was added to the toluene phase in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was left to stand for separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, the water was removed by dewatering with a decanter to obtain an active ester resin in the form of a toluene solution having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, the resin had R in the above formula (1-1) 1 And R is 3 Is a hydrogen atom, Z is a naphthyl group, and l is a structure of 0. The average value k of the repeating units is in the range of 0.5 to 1.0 based on the result of calculation of the reaction equivalent ratio.
Curing agent 2: phenol aralkyl resin having biphenylene skeleton (MEH-7851 SS, manufactured by Ming He Chemie Co., ltd.)
Curing agent 3: phenol hydroxybenzaldehyde type curing agent (MEH-7500, manufactured by Ming He Chemie Co., ltd.)
Curing agent 4: novolak type phenol resin (Sumilite Resin PR-51470, manufactured by Sumitomo electric Wood Co., ltd.)
Curing agent 5: ZYLOCK phenol aralkyl phenol curing agent (MEHC-7800 SS, manufactured by Ming He Chemie Co., ltd.)
Curing agent 6: polyvalent MAR phenol curing agent (SH-002-02 manufactured by Ming He Chemie Co., ltd.)
Curing agent 7: active ester-based curing agent prepared by the following preparation method
(Process for producing active ester-based curing agent)
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 203.0g of 1, 3-benzenedicarboxylic acid dichloride (mole number of acid chloride groups: 2.0 mol) and 1338g of toluene, and the inside of the system was dissolved by nitrogen substitution under reduced pressure. Then, 96.5g (0.67 mol) of α -naphthol and 219.5g (molar number of phenolic hydroxyl groups: 1.33 mol) of dicyclopentadiene phenol resin were charged, and the inside of the system was dissolved by nitrogen substitution under reduced pressure. Thereafter, 400g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while keeping the temperature inside the system at 60℃or lower while purging with nitrogen. Then, stirring was continued under this condition for 1.0 hour. After the completion of the reaction, the mixture was allowed to stand for separation, and the aqueous layer was removed. Then, water was added to the toluene phase in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was left to stand for separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, the water was removed by dewatering with a decanter to obtain an active ester resin in the form of a toluene solution having a nonvolatile content of 65%. As a result of confirming the structure of the obtained active ester resin, the resin had R in the above formula (1-3) 1 And R is 3 Is a hydrogen atom, Z is a naphthyl group, and 1 is 0. 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 of calculation of the reaction equivalent ratio. Specifically, the obtained active ester resin has a structure represented by the following chemical formula. In the following formula, the average value k of the repeating units is 0.5 to 1.0.
(catalyst)
Catalyst 1: tetraphenylphosphonium-4, 4' -sulfonyldiphenol salt
(evaluation of dielectric constant and dielectric loss tangent by Cavity resonance method)
First, a test piece was obtained using the resin composition.
Specifically, the resin compositions prepared in examples and comparative examples were applied to a Si substrate and prebaked at 120℃for 4 minutes to form a resin film having a coating film thickness of 12. Mu.m.
This was heated under nitrogen atmosphere for 90 minutes at 200℃using an oven, and subjected to hydrofluoric acid treatment (immersed in a 2 mass% aqueous hydrofluoric acid solution). After the substrate was taken out of the hydrofluoric acid, the cured film was peeled off from the Si substrate, and this was used as a test piece.
The measuring apparatus used Network Analyzer HP8510C, synthesized sweeperHP83651A and test set HP8517B (both manufactured by agilent technologies (japan) limited). These devices and cylindrical cavity resonators (having an inner diameter of phi 42mm and a height of 30 mm) were mounted.
In a state where the test piece was inserted into the above resonator and in a non-inserted state, the resonance frequency, the 3dB bandwidth, the penetration power ratio, and the like were measured at a frequency of 25 GHz. Then, these measurement results were analytically calculated by software, and dielectric characteristics of dielectric constant (Dk) and dielectric loss tangent (Df) were obtained. In addition, the measurement mode is set to TE 011 A mode.
(measurement of spiral flow)
The resin compositions obtained in examples and comparative examples were injected into a spiral flow measuring mold according to EMMI-1-66 using a low pressure transfer molding machine ("KTS-15" manufactured by Shang Jiuji Co., ltd.) under the conditions of a mold temperature of 175 ℃, an injection pressure of 6.9MPa, and a curing time of 120 seconds, and the flow length was measured.
(gel time (GT))
After the resin compositions of examples and comparative examples were melted on a hot plate heated to 175℃respectively, the time (unit: seconds) until solidification was measured while kneading with a spatula.
(molding shrinkage)
For each of examples and comparative examples, the molding shrinkage (after ASM) after molding (ASM: as Mold) was measured for the obtained resin composition, and after the molding, the molding shrinkage (after PMC) was evaluated under heating conditions (PMC: post Mold Cure) for producing a dielectric substrate by subjecting the resin composition to main curing.
First, a test piece was produced using a low pressure transfer molding machine ("KTS-15" manufactured by Shanghai Seiko Co., ltd.) under the conditions of a mold temperature of 175 ℃, an injection pressure of 6.9MPa, and a curing time of 120 seconds, and a molding shrinkage (after ASM) was obtained according to JIS K6911.
The obtained test piece was subjected to a heating treatment at 175℃for 4 hours, and the molding shrinkage (after ASM) was measured in accordance with JIS K6911.
(glass transition temperature, coefficient of linear expansion)
For each of examples and comparative examples, the glass transition temperature (Tg) and the coefficients of linear expansion (CTE 1, CTE 2) of the cured products of the obtained resin compositions were measured in the following manner. First, a sealing resin composition was injection molded using a low pressure transfer molding machine (KTS-15 manufactured by Shang Jim Co., ltd.) at a mold temperature of 175℃under an injection pressure of 6.9MPa and a curing time of 120 seconds, whereby a test piece of 10mm X4 mm was obtained. Subsequently, the obtained test piece was post-cured at 175℃for 4 hours, and then measured using a thermo-mechanical analyzer (TMA 100, manufactured by Seiko electronic industries Co., ltd.) at a temperature ranging from 0℃to 320℃and a temperature rising rate of 5℃per minute. From the measurement results, a glass transition temperature (Tg), a coefficient of linear expansion (CTE 1) lower than the glass transition temperature, and a coefficient of linear expansion (CTE 2) higher than the glass transition temperature were calculated.
(evaluation of mechanical Strength (flexural Strength/flexural modulus of elasticity))
The resin compositions of examples and comparative examples were injection molded in a mold using a low pressure transfer molding machine ("KTS-30" manufactured by Shang Jiuji Co., ltd.) under the conditions of a mold temperature of 130℃and an injection pressure of 9.8MPa and a curing time of 300 seconds. Thus, a molded article having a width of 10mm, a thickness of 4mm and a length of 80mm was obtained. Next, the obtained molded article was subjected to a temperature of 175℃for 4 hoursPost-curing is performed under conditions. Thus, test pieces for evaluating mechanical strength were produced. Thereafter, the bending strength (N/mm) of the test piece at room temperature (25 ℃) or 260℃was measured at a head speed of 5mm/min in accordance with JIS K6911 2 ) And flexural modulus of elasticity (N/mm) 2 )。
From the results of table 2, it was found that according to the thermosetting resin composition of the second application, a dielectric substrate excellent in high dielectric constant and low dielectric loss tangent, in other words, a dielectric substrate excellent in balance of these characteristics was obtained. Further, it is known that the thermosetting resin composition of the present application has a long flow length of spiral flow and a gel time in an appropriate range, and thus has excellent moldability.
The present application claims priority based on Japanese patent application No. 2021-051748 filed on 3.3 in 2021, japanese patent application No. 2021-172197 filed on 10.21 in 2021, japanese patent application No. 2021-197667 filed on 12.6 in 2021, japanese patent application No. 2021-197669 filed on 12.6 in 2021, japanese patent application No. 2021-197679 filed on 12.6 in 2021, japanese patent application No. 2021-197720 filed on 12.6 in 2021 and Japanese patent application No. 2021-197731 filed on 12.6 in 2021, and the disclosure of which is incorporated herein in its entirety.
Description of the reference numerals
10. Microstrip antenna, 12 dielectric substrate, 14 radiating conductor plate, 16 ground conductor plate, 20' microstrip antenna, 22 dielectric substrate, 24 high dielectric substrate, 26 spacer, a void.

Claims (24)

1. A thermosetting resin composition comprising:
a thermosetting resin;
a high dielectric constant filler having a relative dielectric constant of 10 or more at 25 ℃ and 25 GHz; and
an active ester compound is provided which is a compound of,
the flexural modulus at 25℃measured according to the following procedure was set as FM 25 And the flexural modulus at 260℃was set to FM 260 FM when 25 And FM 260 Meet FM of 0.005 ∈or less 260 /FM 25 ≤0.1，
The flow is as follows:
using a low pressure transfer molding machine, the thermosetting resin composition was injection molded in a mold at a mold temperature of 130℃under an injection pressure of 9.8MPa for a curing time of 300 seconds to obtain a molded article having a width of 10mm, a thickness of 4mm and a length of 80mm,
the obtained molded article was post-cured at 175℃for 4 hours to prepare a test piece,
the flexural modulus of the test piece was measured at room temperature, namely 25℃or 260℃in N/mm in accordance with JIS K6911 2 。
2. The thermosetting resin composition according to claim 1, wherein:
The bending strength at 25℃measured according to JIS K6911 was set as FS 25 And the bending strength at 260℃was set to FS 260 At the time FS 25 And FS 260 Meet the FS of 0.025 ∈ 260 /FS 25 ≤0.2。
3. The thermosetting resin composition according to claim 1 or 2, characterized in that:
the cured product of the thermosetting resin composition has a glass transition temperature of 100-250 ℃.
4. A thermosetting resin composition according to any one of claims 1 to 3, characterized in that:
a cured product of the thermosetting resin composition has a coefficient of linear expansion CTE1 in the range of 5 ppm/DEG C or more and 25 ppm/DEG C or less in the range of not higher than the glass transition temperature, and a coefficient of linear expansion CTE2 in the range of not higher than 320 ℃ or less in the range of not higher than 30 ppm/DEG C or less than 100 ppm/DEG C in the range of not higher than the glass transition temperature.
5. The thermosetting resin composition according to any one of claims 1 to 4, wherein:
the high dielectric constant filler comprises calcium titanate.
6. The thermosetting resin composition according to any one of claims 1 to 5, characterized in that:
in the thermosetting resin composition, the content of the high dielectric constant filler is 30 mass% or more and 90 mass% or less.
7. The thermosetting resin composition according to any one of claims 1 to 6, characterized in that:
the active ester compound includes at least 1 selected from the group consisting of an active ester compound including a dicyclopentadiene type diphenol structure, an active ester compound including a naphthalene structure, an active ester compound including an acetyl compound of a phenol novolac, and an active ester compound including a benzoyl compound of a phenol novolac.
8. The thermosetting resin composition according to any one of claims 1 to 7, characterized in that:
the active ester compound has a structure represented by the following general formula (1),
in the above-mentioned general formula (1),
a is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group,
ar' is a substituted or unsubstituted aryl group,
b is a structure represented by the following general formula (B),
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 having 1 to 6 carbon atoms, or a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 2 valences, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group or a sulfone group, n is an integer of 0 to 4,
k is an average value of repeating units and is in the range of 0.25 to 3.5.
9. The thermosetting resin composition according to any one of claims 1 to 8, characterized in that:
the thermosetting resin comprises an epoxy resin comprising a biphenylene backbone.
10. The thermosetting resin composition according to any one of claims 1 to 9, characterized in that:
further comprises a phenolic curing agent.
11. The thermosetting resin composition according to claim 10, wherein:
the phenolic curing agent comprises a phenolic resin containing a biphenylene skeleton.
12. The thermosetting resin composition according to any one of claims 1 to 11, characterized in that:
for forming part of a high frequency device selected from the group consisting of microstrip antennas, dielectric waveguides and multilayer antennas.
13. A high frequency device characterized by:
a cured product comprising the thermosetting resin composition according to any one of claims 1 to 12.
14. A thermosetting resin composition comprising:
(A) An epoxy resin;
(B) A curing agent; and
(C) A filler with a high dielectric constant,
the epoxy resin (A) contains a biphenyl aralkyl type epoxy resin and/or a biphenyl type epoxy resin other than the biphenyl aralkyl type epoxy resin,
The curing agent (B) contains an active ester curing agent and a phenol curing agent,
the high dielectric constant filler (C) contains at least 1 selected from the group consisting of calcium titanate, barium titanate, strontium titanate, magnesium zirconate, strontium zirconate, bismuth titanate, zirconium titanate, zinc titanate, barium zirconate, calcium titanate, lead titanate, barium magnesium niobate and calcium zirconate,
the high dielectric constant filler (C) is contained in an amount of 30 mass% or more in 100 mass% of the thermosetting resin composition.
15. The thermosetting resin composition of claim 14, wherein:
the high dielectric constant filler (C) is at least 1 selected from the group consisting of calcium titanate, strontium titanate and magnesium titanate.
16. The thermosetting resin composition according to claim 14 or 15, wherein:
the active ester-based curing agent is at least 1 selected from the group consisting of active ester-based curing agents containing dicyclopentadiene-type diphenol structures, active ester-based curing agents containing naphthalene structures, active ester-based curing agents containing an acetylate of phenol novolac, and active ester-based curing agents containing a benzoylate of phenol novolac.
17. The thermosetting resin composition according to any one of claims 14 to 16, wherein:
The active ester curing agent comprises a structure represented by the following general formula (1),
in the general formula (1), A is a substituted or unsubstituted arylene group linked via an aliphatic cyclic hydrocarbon group, ar' is a substituted or unsubstituted aryl group,
b is a structure represented by the following general formula (B),
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 having 1 to 6 carbon atoms, or a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 2 valences, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group or a sulfone group, n is an integer of 0 to 4,
k is an average value of repeating units and is in the range of 0.25 to 3.5.
18. The thermosetting resin composition according to any one of claims 14 to 17, wherein:
also comprises a curing catalyst (D).
19. The thermosetting resin composition according to any one of claims 14 to 18, wherein:
as a material for forming a microstrip antenna.
20. The thermosetting resin composition according to any one of claims 14 to 18, wherein:
as a material for forming the dielectric waveguide.
21. The thermosetting resin composition according to any one of claims 14 to 18, wherein:
As a material for forming an electromagnetic wave absorber.
22. A dielectric substrate, characterized by:
is obtained by curing the thermosetting resin composition according to any one of claims 1 to 12 and 14 to 21.
23. A microstrip antenna, comprising:
the dielectric substrate of claim 22;
a radiation conductor plate provided on one surface of the dielectric substrate; and
and a ground conductor plate provided on the other surface of the dielectric substrate.
24. A microstrip antenna, comprising:
a dielectric substrate;
a radiation conductor plate provided on one surface of the dielectric substrate;
a ground conductor plate provided on the other surface of the dielectric substrate; and
a high dielectric disposed opposite the radiation conductor plate,
the high dielectric is formed from the dielectric substrate of claim 22.
CN202280024604.2A 2021-03-25 2022-03-22 Thermosetting resin composition, high-frequency device, dielectric substrate, and microstrip antenna Pending CN117120504A (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2021-051748 2021-03-25
JP2021-172197 2021-10-21
JP2021-197679 2021-12-06
JP2021-197669 2021-12-06
JP2021-197720 2021-12-06
JP2021-197667 2021-12-06
JP2021-197731 2021-12-06
JP2021197731 2021-12-06
PCT/JP2022/013057 WO2022202781A1 (en) 2021-03-25 2022-03-22 Thermosetting resin composition, high frequency device, dielectric substrate, and microstrip antenna

Publications (1)

Publication Number Publication Date
CN117120504A true CN117120504A (en) 2023-11-24

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CN202280024621.6A Pending CN117083345A (en) 2021-03-25 2022-03-22 Thermosetting resin composition, high-frequency device, dielectric substrate, and microstrip antenna
CN202280024604.2A Pending CN117120504A (en) 2021-03-25 2022-03-22 Thermosetting resin composition, high-frequency device, dielectric substrate, and microstrip antenna
CN202280023625.2A Pending CN117043218A (en) 2021-03-25 2022-03-22 Thermosetting resin composition, dielectric substrate and microstrip antenna

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CN117043218A (en) 2023-11-10

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