Curable composition, electronic component device, high-frequency device, dielectric substrate, and microstrip antenna

Abstract

A curable composition, comprising: a curable component containing an ethylenic unsaturated double bond and capable of radical polymerization; and at least one inorganic filler selected from the group consisting of titanium oxide, calcium titanate, and strontium titanate.

Description

Technical Field

[0001] This disclosure relates to a curable composition, electronic component devices, high-frequency devices, dielectric substrates, and microstrip antennas. Background Technology

[0002] The increasing demands for higher functionality, thinner and smaller electronic devices in recent years have driven the high-density integration of electronic components, leading to higher-density mounting. This has resulted in an increase in the semiconductor packaging used in these devices, further promoting miniaturization. Consequently, it has also driven the use of higher frequencies in the radio waves used for communication within these electronic devices.

[0003] Regarding the miniaturization of semiconductor packaging and handling of high frequencies, high dielectric constant resin compositions for sealing semiconductor elements have been proposed (for example, see Patent Documents 1 to 3). Furthermore, molding resin compositions that balance high dielectric constant and low dielectric loss tangent in the cured product after molding have also been proposed (for example, see Patent Document 4).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-036410

[0007] Patent Document 2: Japanese Patent Application Publication No. 2017-057268

[0008] Patent Document 3: Japanese Patent Application Publication No. 2018-141052

[0009] Patent Document 4: International Publication No. 2022 / 123792 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] In recent years, in order to cope with the increasing number of channels accompanying the diversification of information, the radio waves used in the communication of electronic devices, including semiconductor devices, have become increasingly higher frequency. Along with the higher frequency of radio waves, there is a demand for sealing resin compositions with low dielectric loss tangent.

[0012] If a material with a high dielectric loss tangent is used, the transmitted signal is converted into heat due to dielectric loss, which easily reduces communication efficiency. The amount of dielectric loss caused by the thermal conversion of radio waves transmitted for communication is expressed as the product of the frequency, the square root of the relative permittivity, and the dielectric loss tangent. The transmitted signal is easily converted into heat proportionally to the frequency. Therefore, in order to suppress dielectric loss to a low level in high-frequency radio waves, it is ideal to reduce the dielectric loss tangent.

[0013] For example, in the molding resin composition of Patent Document 4, it is also possible to mold a cured material exhibiting a low dielectric loss tangent. However, considering changes in application and molding method, it is ideal to be able to mold a cured material exhibiting a low dielectric loss tangent in other molding resin compositions as well.

[0014] One aspect of this disclosure is to provide a curable composition capable of forming a curable exhibiting a low dielectric loss tangent, and electronic component devices, high-frequency devices, dielectric substrates, and microstrip antennas using the same.

[0015] Another aspect of this disclosure is to provide a curable composition with excellent flowability for injection molding and an electronic component device using the same.

[0016] Technical means to solve the problem

[0017] This disclosure includes the following embodiments.

[0018] <1> A hardening composition comprising:

[0019] Hardening components containing ethylene-like unsaturated double bonds and capable of free radical polymerization; and

[0020] At least one inorganic filler selected from the group consisting of titanium oxide, calcium titanate and strontium titanate.

[0021] <2> A hardening composition for injection molding and comprising:

[0022] Hardening components containing ethylene unsaturated double bonds and capable of free radical polymerization, and

[0023] Inorganic filler material.

[0024] <3> The curing composition according to <1> or <2>, wherein the curing component comprises at least one compound selected from the group consisting of compounds having a vinylphenyl group and compounds having a maleimide group.

[0025] <4> The curing composition according to any one of <1> to <3>, wherein the curing component comprises a vinylphenyl compound that is liquid at 25°C and a maleimide compound that is solid at 25°C.

[0026] <5> The curing composition according to any one of <1> to <4>, wherein the curing component comprises a compound having a vinylphenyl group and a compound having a maleimide group, the molar content ratio of maleimide group to vinylphenyl group (maleimide group / vinylphenyl group) being 0.05 to 5.0.

[0027] <6> The hardening composition according to any one of <1> to <5> is solid at 25°C.

[0028] <7> The curing composition according to any one of <1> to <6>, wherein the curing component comprises a compound having a vinylphenyl group, the compound having a vinylphenyl group comprising a compound represented by the following formula (b1).

[0029] [Chemistry 1]

[0030]

[0031] (where X) b1 (B represents an organic group, B independently represents a group containing vinylphenyl, and l represents an integer from 1 to 5.)

[0032] <8> The curing composition according to any one of <1> to <7>, wherein the curing component comprises a compound having vinylphenyl, and the compound having vinylphenyl comprises a compound having two or more vinylphenyl groups.

[0033] <9> The curing composition according to any one of <1> to <8>, wherein the curing component comprises a compound having a vinylphenyl group, the compound having a vinylphenyl group comprising a compound represented by the following formula (b3).

[0034] [Chemistry 2]

[0035]

[0036] (In the formula, B) hb Each of the following formulas (Bz) independently represents a hydrogen atom or a group, with at least one B. hb The group represented by the following formula (Bz);

[0037] [Chemistry 3]

[0038]

[0039] (In the formula, * indicates the location of the bond)

[0040] <10> The curing composition according to any one of <1> to <9>, wherein the curing component comprises a compound having a vinylphenyl group, and the compound having a vinylphenyl group comprises a polymer having a vinylphenyl group.

[0041] <11> The curing composition according to any one of <1> to <10>, wherein the curing component comprises a compound having a vinylphenyl group, the compound having a vinylphenyl group comprising a polymer having a structural unit represented by the following formula (Bb).

[0042] [Chemistry 4]

[0043]

[0044] (In the formula, X represents an organic group, B represents a group containing vinylphenyl independently, R represents a substituent independently, l represents an integer from 1 to 5, m represents an integer from 0 to 10; * represents the bond position with other atoms)

[0045] <12> The curing composition according to any one of <1> to <11>, wherein the curing component comprises a compound having a vinylphenyl group, the compound having a vinylphenyl group comprising at least one selected from the group consisting of polymers represented by the following formula (B3-3) and polymers represented by the following formula (B3-7).

[0046] [Chemistry 5]

[0047]

[0048] (In the formula, B) b Each group represented by the following formula (Bz) can be independently represented, where n represents a number from 3 to 5; the benzene ring can have substituents at the positions where substitution is possible;

[0049] [Chemistry 6]

[0050]

[0051] (In the formula, B) b Each group represented by the following formula (Bz) can be independently represented, where n represents a number from 3 to 5; the benzene ring can have substituents at the positions where substitution is possible;

[0052] [Chemistry 7]

[0053]

[0054] (In the formula, * indicates the location of the bond)

[0055] <13> The curing composition according to any one of <1> to <12>, wherein the curing component comprises a compound having a vinyl benzyl group, the compound having a vinyl benzyl group comprising a compound represented by the following formula (A).

[0056] [Chemistry 8]

[0057]

[0058] (In the formula, R) 1 Each R is an independent monovalent organic group, halogen atom, hydrogen atom, or bond position with other structures. 1 At least one of them is vinylbenzyl, R 4 R can be independently a monovalent organic group, a halogen atom, a hydrogen atom, or a bond position with other structures. x1 and R x2 Each is independently a divalent aliphatic hydrocarbon group or a single bond, Ar is a substituted or unsubstituted biphenylene, or a substituted or unsubstituted biphenylene, and n is an integer greater than or equal to 1.

[0059] <14> The curing composition according to any one of <1> to <13>, wherein the dielectric loss tangent of the cured material when cured at 175°C for 6 hours is 0.010 or less.

[0060] <15> The hardening composition according to any one of <1> to <14> is used to form a part of a high-frequency device.

[0061] <16> An electronic component device having electronic components and a hardened copy of a hardening composition according to any one of <1> to <15> that seals at least a portion of said electronic components.

[0062] <17> A high-frequency device having a hardened material of a hardening composition according to any one of <1> to <15>.

[0063] <18> A dielectric substrate is formed by curing a curable composition according to any one of <1> to <15>.

[0064] <19> A microstrip antenna, comprising:

[0065] Dielectric substrate as described in <18>;

[0066] A radiating element is disposed on one side of the dielectric substrate; and

[0067] A ground conductor plate is disposed on the other side of the dielectric substrate.

[0068] The effects of the invention

[0069] According to one aspect of this disclosure, curable compositions capable of forming curables exhibiting low dielectric loss tangents can be provided, as well as electronic component devices, high-frequency devices, dielectric substrates, and microstrip antennas using the same.

[0070] In another aspect of this disclosure, a curable composition with excellent flowability for injection molding and an electronic component device using the same can be provided. Attached Figure Description

[0071] [ Figure 1 [Illustrated diagram] is a schematic diagram illustrating an example of a manufacturing method for an electronic component device using an injection molding machine. Detailed Implementation

[0072] The embodiments of this disclosure will be described. This disclosure is not limited to the following embodiments. The following embodiments can be implemented individually or in combination. Combinations of multiple embodiments are also included in this disclosure.

[0073] In this disclosure, the range of values ​​represented by “~” refers to the range in which the values ​​recorded before and after “~” are respectively the minimum and maximum values.

[0074] In the numerical ranges described in this disclosure, the upper or lower limit of one numerical range can be replaced by the upper or lower limit of another numerical range. The upper or lower limit of the numerical ranges described in this disclosure can be replaced by the values ​​shown in the embodiments.

[0075] A value can be selected from the upper and lower limits described in this disclosure and set as the range of values ​​for that period. The upper and lower limits described in this disclosure can be replaced with the values ​​shown in the embodiments.

[0076] In this disclosure, each component may contain multiple equivalent substances. When multiple equivalent substances are present in the composition, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition.

[0077] In this disclosure, each structure in the polymer may include multiple equivalent structures. When multiple equivalent structures exist in the polymer, unless otherwise specified, the content or percentage of each structure refers to the total content or percentage of the multiple structures present in the polymer.

[0078] In this disclosure, the particles corresponding to each component may comprise a variety of particles. When a variety of particles corresponding to each component are present in the composition, unless otherwise specified, the particle size of each component refers to a value relating to the mixture of the various particles present in the composition.

[0079] The curing composition disclosed herein is a concept comprising the curing composition of the first embodiment described below and the curing composition of the second embodiment.

[0080] <Curing Composition>

[0081] [First Implementation Form]

[0082] The curing composition of the first embodiment of this disclosure is a composition comprising: a curing component containing ethylene unsaturated double bonds and capable of free radical polymerization (hereinafter also referred to as a specific curing component); and at least one inorganic filler selected from the group consisting of titanium oxide, calcium titanate and strontium titanate (hereinafter also referred to as a specific inorganic filler).

[0083] The curable composition of the first embodiment contains specific curing components and specific inorganic fillers. This allows for the formation of a cured product exhibiting a low dielectric loss tangent. The curable composition of this disclosure can be used in various molding methods such as injection molding, transfer molding, and compression molding. For example, the curable composition of this disclosure can be used for injection molding, and by using specific curing components, the curable composition tends to have a low viscosity during injection molding compared to using thermoplastic resins, and tends to be able to be injection molded under low pressure.

[0084] [Second Implementation Form]

[0085] The curable composition of the second embodiment of this disclosure is a composition comprising a curable component containing ethylene unsaturated double bonds and capable of free radical polymerization and an inorganic filler, said composition being suitable for injection molding.

[0086] The curable composition in the second embodiment contains specific curable components and inorganic fillers. By using the specific curable components, it exhibits excellent flowability, and compared to using thermoplastic resins, the curable composition tends to have a low viscosity during injection molding, and tends to be able to be injection molded under low pressure.

[0087] For example, in previously widely used epoxy resin compositions, the epoxy resin undergoes a curing reaction that opens the ring and generates hydroxyl groups. Hydroxyl groups are polar groups, thus resulting in a high dielectric loss tangent in the cured product. In contrast, under specific curing components, polar groups like hydroxyl groups are not generated, and there is a tendency to suppress the dielectric loss tangent of the cured product to a low level. Therefore, the curing compositions disclosed herein can also be preferably applied to high-frequency devices requiring a low dielectric loss tangent.

[0088] The curable composition disclosed herein can be liquid or solid at 25°C. From the viewpoint of handling such as conveying and mixing, it can be solid at 25°C.

[0089] The term "liquid" simply refers to any state that can be measured using a viscometer.

[0090] The specific curing component contained in the curing composition is a component that contains ethylene unsaturated double bonds and is capable of free radical polymerization.

[0091] Examples of specific curing components include: compounds containing acrylic acid groups, compounds containing methacrylic acid groups, compounds containing vinyl groups, and compounds containing maleimide groups.

[0092] Specific hardening ingredients can be used alone or in combination with two or more.

[0093] The specific curing component is preferably at least one compound selected from the group consisting of compounds having a vinylphenyl group (hereinafter also referred to as "vinylphenyl compounds") and compounds having a maleimide group (hereinafter also referred to as "maleimide compounds"). Therefore, when producing a cured product of the curing composition, there is a tendency to reduce molding shrinkage.

[0094] The specific curing components preferably include a vinylphenyl compound and a maleimide compound, more preferably a vinylphenyl compound that is liquid at 25°C and a maleimide compound that is solid at 25°C. The vinylphenyl compound and the maleimide compound exhibit excellent reactivity, thus allowing for a lower heating temperature compared to polymerization using only the vinylphenyl compound to produce a cured product. Furthermore, compared to conventional epoxy resin compositions, the curing composition disclosed herein also allows for a lower heating temperature for curing.

[0095] [Compounds containing vinylphenyl groups]

[0096] A vinylphenyl compound is a compound having at least one vinylphenyl group. For example, a vinylphenyl compound may have 1 to 20, 1 to 15, or 1 to 10 vinylphenyl groups. A vinylphenyl compound may be used alone or in combination with two or more.

[0097] Vinylphenyl can be represented by any of the following formulas. From the viewpoint of obtaining a cured material with low dielectric constant and low dielectric loss tangent, vinylphenyl compounds are preferably compounds containing groups having the group represented by formula (p). * indicates the bonding position with other atoms.

[0098] [Chemistry 9]

[0099]

[0100] The proportion of the group represented by formula (p) relative to the total amount of the groups represented by formula (m) and formula (o) in the total amount of the vinylphenyl compound is preferably 40 mol% or more, and can be 50 mol% or more, 60 mol% or more, or 70 mol% or more. Alternatively, the proportion of the group represented by formula (p) can be 10 mol% or more, 20 mol% or more, or 30 mol% or more.

[0101] The larger the proportion of the group represented by formula (p), the lower the dielectric constant and dielectric loss tangent of the hardened material tend to be.

[0102] The molar ratio of the groups represented by formula (p), the groups represented by formula (m), and the groups represented by formula (o) in the total amount of vinylphenyl compounds contained in the curing composition (groups represented by formula (p): groups represented by formula (m): groups represented by formula (o)) can be, for example, 40-100:0-60:0-60, 70-90:0:10-30 or 40-60:40-60:0.

[0103] Vinylphenyl compounds can be compounds having a vinylphenyl methyl group (also called "vinylbenzyl"). In this disclosure, compounds having a vinylbenzyl group are sometimes referred to as "vinylbenzyl compounds." Vinylbenzyl compounds are examples of vinylphenyl compounds. Vinylphenyl compounds can also be compounds having a vinylphenyl methyloxy group (also called "vinylbenzyl ether group"). In this disclosure, compounds having a vinylbenzyl ether group are sometimes referred to as "vinylbenzyl ether compounds." Vinylbenzyl ether compounds are examples of vinylbenzyl compounds and vinylphenyl compounds.

[0104] Vinylphenyl compounds may also possess aromatic rings in addition to vinylphenyl groups. Vinylphenyl compounds may have only one aromatic ring or two or more aromatic rings. The aromatic rings may be aromatic hydrocarbon rings or aromatic heterocyclic rings. The aromatic rings may be monocyclic or condensed polycyclic. Examples of aromatic hydrocarbon rings include: benzene, naphthalene, anthracene, condensed tetraphenylene, fluorene, phenanthrene, indene, dihydroindene, biphenylene, etc. Examples of aromatic heterocyclic rings include: pyridine, pyrazine, quinoline, isoquinoline, acridine, phenoline, furan, pyrrole, thiophene, carbazole, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxadiazole, benzothiadiazole, benzotriazole, benzothiophene, etc. From the viewpoint of the dielectric properties of the cured material, the aromatic rings can be aromatic hydrocarbon rings or condensed polycyclic aromatic hydrocarbon rings. From the viewpoint of dielectric constant and dielectric loss tangent, aromatic rings, such as fluorene and indene, are preferred. In the case of vinylphenyl compounds containing indene, there is a tendency to obtain cured products exhibiting lower dielectric constant and dielectric loss tangent.

[0105] In several embodiments, the vinylphenyl compound comprises a compound having two or more vinylphenyl groups. The compound having two or more vinylphenyl groups can be a monomer or a polymer.

[0106] Vinylphenyl compounds can be monomers or polymers capable of free radical polymerization. Vinylphenyl compounds, for example, comprise monomers having a vinylphenyl group. In this disclosure, monomers having a vinylphenyl group are sometimes referred to as "vinylphenyl-containing monomers." Vinylphenyl compounds, for example, comprise polymers having a vinylphenyl group. In this disclosure, polymers having a vinylphenyl group are sometimes referred to as "vinylphenyl-containing polymers."

[0107] In this disclosure, the monomer may be a repeating compound that does not contain structural units. The polymer may be a repeating compound that contains structural units. The polymer may be a polymer with a low degree of polymerization (i.e., an oligomer) or a polymer with a high degree of polymerization.

[0108] Examples of vinylphenyl compounds include those represented by formula (b1) below.

[0109] [Chemistry 10]

[0110]

[0111] In equation (b1), X b1 B represents an organic group, B represents a group containing vinylphenyl groups independently, and l represents an integer from 1 to 5.

[0112] The term "independently" means that when l is 2 or more and there are multiple Bs, the multiple Bs can be the same "group containing vinylphenyl", or they can be some or all of different "groups containing vinylphenyl". "Independently" does not prevent l from being 1, and the structural unit represented by formula (b1) can have one "group containing vinylphenyl". The same applies to "independently" in this disclosure.

[0113] X b1 The represented organic group may be a group containing at least one carbon atom. In the case where the compound represented by formula (b1) is a vinylphenyl-containing monomer, as X... b1 The organic group represented may include, for example, an aromatic cyclic group. Examples of aromatic rings contained in an aromatic cyclic group are as described above. In the case where the compound represented by formula (b1) is a monomer containing a vinylphenyl group, l may be 1 to 3.

[0114] When the compound represented by formula (b1) is a polymer containing vinylphenyl, X b1 The organic groups represented are polymers.

[0115] (Monomers containing vinylphenyl)

[0116] In several embodiments, the vinylphenyl compound comprises a vinylphenyl-containing monomer. In several embodiments, the vinylphenyl-containing monomer may comprise a monomer having two vinylphenyl groups, and further comprise at least one selected from the group consisting of monomers having one vinylphenyl group and monomers having three vinylphenyl groups; or may comprise a monomer having two vinylphenyl groups, a monomer having one vinylphenyl group, and a monomer having three vinylphenyl groups. When the vinylphenyl-containing monomer comprises two or more vinylphenyl-containing monomers, the average number of vinylphenyl groups in the vinylphenyl-containing monomer is, for example, 1.4 to 2.8, 1.6 to 2.7, or 1.8 to 2.6.

[0117] Monomers containing vinylphenyl groups may also have aromatic rings other than the benzene ring contained in the vinylphenyl group. Monomers containing vinylphenyl groups may have only one aromatic ring or two or more aromatic rings. Examples of aromatic rings are described above.

[0118] Monomers containing vinylphenyl groups may, for example, comprise one to three vinylphenyl groups having an aromatic ring other than the benzene ring contained in the vinylphenyl group and bonded directly or via a linker to the aromatic ring; may comprise a monomer having an aromatic hydrocarbon and bonded directly or via a linker to the aromatic hydrocarbon; or may comprise a monomer having an indene ring and bonded directly or via a linker to the indene ring. The linker may, for example, be a group selected from the group consisting of alkylene, oxy, thio, sulfonyl, sulfinyl, carbonyl, carbonyloxy, imino, and groups composed of two or more of these groups having 1 to 5 carbon atoms. Furthermore, the phrase "having an aromatic ring and bonded to one to three vinylphenyl groups via a linker" means "having an aromatic ring and one to three 'vinylphenyl groups bonded to the aromatic ring and bonded to the linker'".

[0119] Monomers containing vinylphenyl groups can replace aromatic rings or have saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, or groups containing heteroatoms, along with aromatic rings.

[0120] From the viewpoint of curability and processability, the weight average molecular weight (Mw) of the vinylphenyl-containing monomers is, for example, 200–2000, 200–1000, 200–800, 250–750, or 300–700.

[0121] In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) refer to values ​​determined by gel permeation chromatography (GPC) using polystyrene conversion. Specifically, the weight-average molecular weight (Mw) in this disclosure can be determined by the method described in the examples. The number-average molecular weight (Mn) in this disclosure can be determined in the same manner as the method for determining Mw described in the examples.

[0122] In the case where the monomer containing vinylphenyl includes the compound represented by formula (b1), it may include a compound in formula (b1) where l is 2, and further include at least one selected from the group consisting of compounds in formula (b1) where l is 1 and compounds in formula (b1) where l is 3; or it may include a compound in formula (b1) where l is 2, a compound in formula (b1) and a compound in formula (b1) where l is 3.

[0123] When the monomer containing vinylphenyl comprises compounds represented by various formulas (b1), the average value of l in the compounds represented by formula (b1) is, for example, 1.4–2.8, 1.6–2.7, or 1.8–2.6.

[0124] In several embodiments, the vinylphenyl compound comprises the compound represented by formula (b2) below. When the vinylphenyl compound comprises the compound represented by formula (b2) below, there is a tendency to obtain better heat resistance and a lower coefficient of linear thermal expansion.

[0125] [Chemistry 11]

[0126]

[0127] In equation (b2), X b2 B represents an aromatic hydrocarbon group. p Each of the following formulas (Ph) represents a group independently, L represents a direct bond or a linking group independently, and l represents an integer from 1 to 3.

[0128] [Chemistry 12]

[0129]

[0130] In the formula (Ph), * indicates the location of the bond.

[0131] Examples of aromatic hydrocarbon rings contained in aromatic hydrocarbon ring groups are as described above. X b2For example, it can be a condensed polycyclic aromatic hydrocarbon cyclic group. Examples of linking groups are as described above. Linking groups can be, for example, alkylene or methylene. Monomers containing vinylphenyl groups can, for example, include compounds in formula (b2) where l is 2, and further include at least one selected from the group consisting of compounds where l is 1 and l is 3; or can include compounds where l is 2, l is 1 and l is 3.

[0132] When the monomer containing vinylphenyl comprises compounds represented by multiple formulas (b2), the average value of l in the compounds represented by formula (b2) is, for example, 1.4–2.8, 1.6–2.7, or 1.8–2.6. Furthermore, L stands for "direct bond," referring to X... b2 With B p Direct bonds. The same applies to "direct bonds" in this disclosure.

[0133] From the viewpoint of obtaining a hardened material with low dielectric constant and low dielectric loss tangent, the group represented by formula (Ph) may include the group represented by formula (p).

[0134] In several embodiments, the vinylphenyl compound comprises a compound represented by formula (b3) below. When the vinylphenyl compound comprises a compound represented by formula (b3) below, there is a tendency to obtain better heat resistance and a lower coefficient of linear thermal expansion, and consequently, a lower dielectric constant and dielectric loss tangent.

[0135] [Chemistry 13]

[0136]

[0137] In formula (b3), B hb Each of the following formulas (Bz) independently represents a hydrogen atom or a group, with at least one B. hb It is the group represented by the following formula (Bz).

[0138] [Chemistry 14]

[0139]

[0140] In equation (Bz), * indicates the bond position.

[0141] The vinylphenyl-containing monomer may include compounds having two groups represented by formula (Bz) in formula (b3), and further include at least one selected from the group consisting of compounds having one group represented by formula (Bz) and compounds having three groups represented by formula (Bz); or may include compounds having two groups represented by formula (Bz), compounds having one group represented by formula (Bz), and compounds having three groups represented by formula (Bz). When the vinylphenyl-containing monomer includes multiple compounds represented by formula (b3), the average number of groups represented by formula (Bz) in the compounds represented by formula (b3) is, for example, 1.4 to 2.8, 1.6 to 2.7, or 1.8 to 2.6.

[0142] From the viewpoint of obtaining a hardened material with low dielectric constant and low dielectric loss tangent, the group represented by formula (Bz) may include a group in which the vinyl group is bonded to the benzene ring at a para position relative to the methylene group on the benzene ring.

[0143] There are no particular limitations on the method for synthesizing monomers containing vinylphenyl groups. For example, when the monomer containing vinylphenyl groups is a compound represented by formula (b2), a method can be described by reacting an aromatic hydrocarbon with styrene having a halogenated methyl group in the presence of a basic compound. In the case of synthesis by said method, the compound represented by formula (b2) has a methylene group as a linking group.

[0144] Examples of styrene containing halogenated methyl groups include o-chloromethylstyrene, m-chloromethylstyrene, and p-chloromethylstyrene; these can be used alone or in combination of two or more. Examples of basic compounds include alkali metal hydroxides and alkali metal alkoxides. A phase transfer catalyst can be used in the reaction. Examples of phase transfer catalysts include tetrabutylammonium bromide and tetrabutylammonium bromide. The reaction can be carried out in a solvent. The reaction can be carried out under heating and stirring. Polymerization inhibitors can be added to the reaction system. The obtained product can be purified as needed using known methods such as concentration, reprecipitation, and washing.

[0145] (Polymers containing vinylphenyl)

[0146] In several embodiments, the vinylphenyl compound comprises a polymer containing vinylphenyl groups. The vinylphenyl compound may comprise a polymer having two vinylphenyl groups; or it may comprise a polymer having three or more vinylphenyl groups. Examples of vinylphenyl-containing polymers include polymers having a hydrocarbon backbone and vinylphenyl groups; polymers having a phenolic resin-type backbone and vinylphenyl groups. Examples of polymers having a hydrocarbon backbone include: polyolefins, vinyl polymers, acrylic polymers, polydicyclopentadiene, etc. Examples of phenolic resins include: phenolic varnish-type phenolic resins, aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, triphenylmethane-type phenolic resins, and resins in which the phenol structure replaces the phenol structure or includes a naphthol structure along with the phenol structure.

[0147] From a processability perspective, the weight-average molecular weight (Mw) of the vinylphenyl-containing polymer is, for example, 300–50,000, 500–30,000, 1,000–10,000, or more than 2,000–10,000. From the viewpoint of improving the flowability of the curable composition, the weight-average molecular weight (Mw) may be 5,000 or less or 2,500 or less.

[0148] In several embodiments, the vinylphenyl compound may comprise a polymer having the structure represented by the following formula (Bb).

[0149] [Chemistry 15]

[0150]

[0151] In formula (Bb), X represents an organic group, B represents a group containing vinylphenyl groups independently, R represents a substituent independently, l represents an integer from 1 to 5, and m represents an integer from 0 to 10. * indicates the bond position with other atoms.

[0152] The organic group represented by X may be a group containing at least one carbon atom, for example, it may be a group containing at least one of the group consisting of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups and aromatic heterocyclic groups.

[0153] The organic group represented by X may also include linking groups containing heteroatoms, substituents containing heteroatoms, etc.

[0154] Examples of substituents represented by R include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl.

[0155] m can represent integers from 0 to 5, integers from 0 to 2, or 0.

[0156] In several embodiments, the vinylphenyl compound comprises a polymer having the structure represented by the following formula (B1).

[0157] [Chemistry 16]

[0158]

[0159] In equation (B1), X B1 The symbol represents an organic group, B represents a group containing vinylphenyl, R represents a substituent independently, and m represents an integer from 0 to 10. * indicates the bond position with other atoms.

[0160] X B1 X has the same meaning as in equation (Bb). Furthermore, B, R, and m in equation (B1) have the same meaning as B, R, and m in equation (Bb).

[0161] In several embodiments, the vinylphenyl compound comprises a polymer represented by formula (B2) below. When the vinylphenyl compound comprises a polymer represented by formula (B2) below, there is a tendency to obtain superior heat resistance and a lower coefficient of linear thermal expansion.

[0162] [Chemistry 17]

[0163]

[0164] In equation (B2), X B2 Each of the following can independently represent a benzene ring or a naphthalene ring, and each of the following can independently represent an organogroup: B p Each of the following groups (Ph) represents a group independently, L represents a direct bond or a linking group independently, R represents a substituent independently, m represents an integer from 0 to 5 independently, and n represents a number from 2 to 10.

[0165] [Chemistry 18]

[0166]

[0167] In the formula (Ph), * indicates the location of the bond.

[0168] The organic group represented by Y can be a group containing at least one carbon atom, such as: substituted or unsubstituted alkylene groups such as methylene and ethylene; substituted or unsubstituted cycloalkylene groups such as tetrahydrodicyclopentadiene; substituted or unsubstituted arylalkylene groups such as phenylmethylene; substituted or unsubstituted divalent organic groups containing alkylene and arylene groups, etc.

[0169] From the viewpoint of obtaining a hardened material with low dielectric constant and low dielectric loss tangent, the group represented by formula (Ph) may include the group represented by formula (p).

[0170] Examples of linkages represented by L include: alkylene, oxy, thio, sulfonyl, sulfinyl, carbonyl, carbonyloxy, imino, and groups formed by combining two or more of these.

[0171] Examples of substituents represented by R include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The substituent can be an alkyl group having 1 to 5 carbon atoms, or it can be methyl.

[0172] m can represent integers from 0 to 4, integers from 0 to 2, or 0, respectively, independently.

[0173] n is the average value of the polymer represented by formula (B2). n can represent, for example, a number from 2 to 8 or a number from 3 to 5.

[0174] In several embodiments, the vinylphenyl compound may comprise at least one polymer selected from the group consisting of polymers represented by the following formula.

[0175] [Chemistry 19]

[0176]

[0177] [Chemistry 20]

[0178]

[0179] In the various formulas, B p Each group in the formula (Ph) represents a substituent independently, L represents a direct bond or a linking group independently, and n represents a number from 2 to 10. The benzene ring and the naphthalene ring may each have substituents independently at the positions where substitution is possible.

[0180] From the viewpoint of obtaining a hardened material with low dielectric constant and low dielectric loss tangent, the group represented by formula (Ph) may include the group represented by formula (p).

[0181] Examples of linking groups represented by L in various formulas include: alkylene, oxy, thio, sulfonyl, sulfinyl, carbonyl, carbonyloxy, imino, and groups selected from two or more of these. From the viewpoint of obtaining good traceability, the linking group may contain an oxygen group. For example, the linking group may contain a methyleneoxy group, in which case the polymer represented by the formula contains B. p The structure represented by -CH2-O-* (* indicates the bonding position with other atoms).

[0182] When the benzene ring and naphthalene ring in the various formulas have substituents, examples of substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The substituent can be an alkyl group having 1 to 5 carbon atoms, or it can be methyl. Alternatively, the benzene ring and naphthalene ring in the various formulas may be unsubstituted, or except for *-LB. p (* indicates the bonding position with other atoms) It has no substituents.

[0183] n is the average value of the polymer represented by each formula. For example, n can represent a number from 2 to 8 or a number from 3 to 5.

[0184] When the vinylphenyl compound comprises at least one polymer selected from the group consisting of polymers represented by formula (B2-1) to polymers represented by formula (B2-11), it tends to readily obtain excellent heat resistance and a low coefficient of linear thermal expansion. When the vinylphenyl compound comprises at least one polymer selected from the group consisting of polymers represented by formula (B2-3) and polymers represented by formula (B2-7), it tends to readily obtain a low dielectric constant and dielectric loss tangent. In particular, when the vinylphenyl compound comprises a polymer represented by formula (B2-3), it tends to obtain an even lower dielectric constant and dielectric loss tangent. In particular, when the vinylphenyl compound comprises a polymer represented by formula (B2-7), it tends to readily obtain good tracking resistance, and the curable composition exhibits good flowability.

[0185] In several embodiments, the vinylphenyl compound comprises at least one selected from the group consisting of polymers represented by formula (B3-3) and polymers represented by formula (B3-7).

[0186] [Chemistry 21]

[0187]

[0188] In formula (B3-3), B b Each group represented by the following formula (Bz) is independently represented, where n represents a number from 3 to 5.

[0189] [Chemistry 22]

[0190]

[0191] In formula (B3-7), B b Each group represented by the following formula (Bz) is independently represented, where n represents a number from 3 to 5.

[0192] [Chemistry 23]

[0193]

[0194] In equation (Bz), * indicates the bond position.

[0195] From the viewpoint of obtaining a hardened material with low dielectric constant and low dielectric loss tangent, the group represented by formula (Bz) may include a group in which the vinyl group is bonded to the benzene ring at a para position relative to the methylene group on the benzene ring.

[0196] There are no particular limitations on the method for synthesizing polymers containing vinylphenyl groups. For example, when the polymer containing vinylphenyl groups is a compound represented by formula (B2-1), a method can be listed that involves reacting a phenolic resin with styrene having a halogenated methyl group in the presence of a basic compound. In the case of synthesis by said method, the compound represented by formula (B2-1) has a methyleneoxy group as a linking group.

[0197] Examples of styrene with halogenated methyl groups, basic compounds, and phase transfer catalysts are described above. The reaction can be carried out in a solvent. The reaction can be carried out under heating and stirring. Polymerization inhibitors can be added to the reaction system. The obtained product can be purified as needed using known methods such as concentration, reprecipitation, and washing.

[0198] Examples of phenolic resins include: phenolic varnish-type phenolic resins, aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, triphenylmethane-type phenolic resins, and resins in which the phenol structure is replaced or where the naphthol structure is included along with the phenol structure. Commercially available phenolic resins can be used.

[0199] From the viewpoint of processability of the curable composition, the weight average molecular weight (Mw) of the phenolic resin is, for example, 300–30,000, 500–10,000, or 1,000–5,000. From the viewpoint of processability, the number average molecular weight (Mn) of the phenolic resin is, for example, 200–10,000, 500–5,000, or 1,000–2,000.

[0200] From the viewpoint of the heat resistance and linear thermal expansion coefficient of the cured product, the hydroxyl equivalent of phenolic resins is, for example, 50 g / eq to 500 g / eq, 100 g / eq to 400 g / eq, or 150 g / eq to 300 g / eq. The hydroxyl equivalent can be determined according to the method of Japanese Industrial Standards (JIS) K 0070:1992.

[0201] Vinylbenzyl compounds may include compounds represented by the following formula (A).

[0202] [Chemistry 24]

[0203]

[0204] In equation (A), R 1 Each R is an independent monovalent organic group, halogen atom, hydrogen atom, or bond position with other structures. 1 At least one of them is vinylbenzyl, R 4 R can be independently a monovalent organic group, a halogen atom, a hydrogen atom, or a bond position with other structures. x1 and R x2 Each is independently a divalent aliphatic hydrocarbon group or a single bond, Ar is a substituted or unsubstituted biphenylene, or a substituted or unsubstituted biphenylene, and n is an integer greater than or equal to 1.

[0205] In equation (A), R 1 Each R is an independent bond position of a monovalent organic group, halogen atom, hydrogen atom, or other bond. 1 At least one of them is vinylbenzyl. R 1 The monovalent organic group represented is preferably a saturated or unsaturated, chain-like or cyclic hydrocarbon group. Multiple R 1 At least one of them is vinylbenzyl. The remaining R 1 The monovalent organic group can have 1–30, 1–12, or 1–4 carbon atoms. Specifically, R 1 The monovalent organic group represented can be an alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, etc. As for halogen atoms, examples include fluorine, chlorine, bromine, iodine, etc. R 1 The bonding site can be a bonding site with a unit having a biphenyl group, a bonding site with a unit having a vinyl benzyl group, etc. In formula (A), multiple R... 1 They can be the same or different. In formula (A), it is preferable to have multiple Rs. 1 At least one of them is vinylbenzyl, and the remaining R 1 Some or all of them are hydrogen atoms.

[0206] In equation (A), R 4 Each can be independently a monovalent organic group, a halogen atom, a hydrogen atom, or a bond position with other bonds. That is, R 4 R can be independently 1 The basis is explained in equation (A). In equation (A), multiple R... 4 They can be completely identical, or partially or completely different. In equation (A), R 4 Preferably, it is partially or entirely composed of a monovalent organic group or hydrogen atom, more preferably an alkyl group or hydrogen atom having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, and even more preferably a hydrogen atom. 4 It can consist entirely of hydrogen atoms. Furthermore, R 4Some or all of them may be groups that do not contain ethylene double bonds.

[0207] In equation (A), R x1 and R x2 Each is independently a divalent aliphatic hydrocarbon group or a single bond. The divalent aliphatic hydrocarbon group can be saturated or unsaturated, chain or alicyclic, preferably a saturated chain hydrocarbon group, specifically, it can be an alkyl group. The number of carbon atoms in the divalent aliphatic hydrocarbon group can be, for example, 1–30, 1–20 or 1–10, and from the viewpoint of dielectric properties, it can be 1–8, 1–6 or 1–4. Examples include methylene, ethylene, trimethylene, isopropylene, n-butylene, isobutylene, tert-butylene, and sec-butylene. In formula (A), R x1 and R x2 They can be the same or different. In equation (A), R x1 and R x2 Each is preferably a methylene group or a single bond, and more preferably a methylene group.

[0208] In formula (A), Ar is a substituted or unsubstituted biphenylene or a substituted or unsubstituted phenylene. When the biphenylene or phenylene has substituents, the substituents can be monovalent organic groups, halogen atoms, etc. The monovalent organic group can be an alkyl group, or an alkyl group having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, etc. The biphenylene or phenylene may contain functional groups containing heteroatoms as substituents; from the viewpoint of dielectric properties, it is preferable that it does not contain functional groups containing heteroatoms.

[0209] In formula (A), n is an integer of 1 or more. n is an integer and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 4. n may be 1. In addition, in general formula (1), n ​​may be an integer suitably determined according to the weight average molecular weight (Mw) of the vinylbenzyl compound described later.

[0210] Vinylbenzyl compounds are not limited by their synthetic methods; for example, they can be obtained by reacting substituted or unsubstituted indene, substituted or unsubstituted compounds having one or two phenylene groups, and substituted or unsubstituted vinylbenzyl halides. Examples of substituents include: monovalent organic groups such as alkyl groups having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, halogen atoms, hydrogen atoms, etc.

[0211] In formula (A), the bonding site between the indene ring and the vinyl benzyl group is preferably at position 1 of the indene ring. Furthermore, the indene ring and R... x1 and R x2The bonding site is preferably at position 1 or 2 of the indene ring. Furthermore, the vinylbenzyl group can be any one of ortho-vinylbenzyl, meta-vinylbenzyl, and para-vinylbenzyl, more preferably para-vinylbenzyl. In formula (A), the vinylbenzyl group is preferably partially or entirely para-vinylbenzyl.

[0212] Preferably, the compound has the following structure: having at least one vinylbenzyl group bonded to one inden ring in formula (A). For example, a compound represented by the following formula (A-1). In formula (A-1), details regarding each functional group and n are omitted as they are common to formula (A). In formula (A-1), R... 1 and R 4 More preferably, it is partially or entirely composed of alkyl groups or hydrogen atoms having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, and even more preferably, hydrogen atoms. 1 and R 4 It can consist entirely of hydrogen atoms.

[0213] [Chemistry 25]

[0214]

[0215] For example, vinylbenzyl compounds may include compounds represented by the following formula (1).

[0216] [Chemistry 26]

[0217]

[0218] In equation (1), R 1 Each R is an independent bond position of a monovalent organic group, halogen atom, hydrogen atom, or other bond. 1 At least one of them is vinylbenzyl, R 4 R represents, independently, a monovalent organic group, a halogen atom, a hydrogen atom, or a bond position with other bonds. x1 and R x2 Each is independently a divalent aliphatic hydrocarbon group or a single bond, and Ar is a substituted or unsubstituted biphenylene or a substituted or unsubstituted phenylene.

[0219] Details regarding each functional group are omitted as they are common to equation (A).

[0220] As an example, compounds represented by the following formula (1-1) can be listed. In formula (1-1), details regarding each functional group are omitted as they are common to formula (A). In formula (1-1), R... 1 and R 4 More preferably, it is partially or entirely composed of alkyl groups having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, or hydrogen atoms, and even more preferably, hydrogen atoms.1 and R 4 It can consist entirely of hydrogen atoms.

[0221] [Chemistry 27]

[0222]

[0223] Vinylbenzyl compounds may include compounds represented by the following formula (2).

[0224] [Chemistry 28]

[0225]

[0226] In equation (2), R 1 Each can be independently a monovalent organic group, a halogen atom, or a hydrogen atom, R 4 Each can be independently a monovalent organic group, a halogen atom, or a hydrogen atom, R 5 and R 6 Each is independently a divalent aliphatic hydrocarbon group or a single bond, R 7 and R 8 Each can be independently a monovalent organic group, a halogen atom, or a hydrogen atom.

[0227] Details regarding each functional group are omitted as they are common to equation (A).

[0228] As an example, compounds represented by the following formula (2-1) can be listed. In formula (2-1), details regarding each functional group are omitted as they are common to formula (A). In formula (2-1), R... 1 and R 4 More preferably, it is partially or entirely composed of alkyl groups having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, or hydrogen atoms, and even more preferably, hydrogen atoms. 1 and R 4 It can consist entirely of hydrogen atoms.

[0229] [Chemistry 29]

[0230]

[0231] Vinylbenzyl compounds may include compounds represented by the following formula (3).

[0232] [Chemistry 30]

[0233]

[0234] In equation (3), R 1 Each can be independently a monovalent organic group, a halogen atom, or a hydrogen atom, R 4 Each can be independently a monovalent organic group, a halogen atom, or a hydrogen atom, R 11and R 12 Each is independently a divalent aliphatic hydrocarbon group or a single bond, R 13 It can be a monovalent organic group, a halogen atom, or a hydrogen atom.

[0235] Details regarding each substituent are omitted as they are common to formula (A).

[0236] As an example, compounds represented by the following formula (3-1) can be listed. In formula (3-1), details regarding each functional group are omitted as they are common to formula (A). In formula (3-1), R... 1 and R 4 More preferably, it is partially or entirely composed of alkyl groups having 1 to 30, 1 to 12, or 1 to 4 carbon atoms, or hydrogen atoms, and even more preferably, hydrogen atoms. 1 and R 4 It can consist entirely of hydrogen atoms.

[0237] [Chemistry 31]

[0238]

[0239] The following describes the weight-average molecular weight (Mw) of vinyl benzyl compounds. The weight-average molecular weight (Mw) of vinyl benzyl compounds can be 100,000 or less, 50,000 or less, 10,000 or less, 5,000 or less, or 2,000 or less. Within these ranges, better solvent solubility and coatability can be obtained in the cured composition state, and better formability and flexibility can be obtained in the coating film, semi-cured product, or cured product state. The weight-average molecular weight (Mw) of vinyl benzyl compounds can be 400 or more, 500 or more, 800 or more, or 1,000 or more. Within these ranges, better solvent solubility and coatability can be obtained in the cured composition state, and better formability and flexibility can be obtained in the coating film, semi-cured product, or cured product state. For example, the weight average molecular weight (Mw) of vinylbenzyl compounds can be 400–100,000, 400–50,000, 500–10,000, 800–5,000, or 1,000–2,000.

[0240] Vinylphenyl compounds can be used alone or in combination with two or more.

[0241] When a vinylphenyl compound contains a vinylbenzyl compound, the content of the vinylbenzyl compound is, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total mass of the vinylphenyl compound. The upper limit for the content of the vinylbenzyl compound may be 100% by mass.

[0242] When a vinylbenzyl ether compound is included in a vinylphenyl compound, the content of the vinylbenzyl ether compound is, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the mass of the vinylphenyl compound. The upper limit of the content of the vinylbenzyl ether compound can be 100% by mass. When a curing composition includes a vinylbenzyl ether compound, there is a tendency for improved traceability.

[0243] [Compounds containing maleimide groups]

[0244] Maleimide compounds are compounds having at least one maleimide group. Maleimide compounds may have, for example, 1 to 20, 1 to 15, or 1 to 10 maleimide groups. Maleimide compounds may be used alone or in combination with two or more.

[0245] Maleimide compounds can be liquid or solid at 25°C.

[0246] In addition, maleimide compounds can also be monomers or polymers that can undergo free radical polymerization.

[0247] In some embodiments, the maleimide compound comprises a compound having two maleimide groups. In this disclosure, a compound having two maleimide groups is sometimes referred to as a "bismaleimide". In some embodiments, the maleimide compound comprises a compound having three or more maleimide groups.

[0248] The maleimide group can be represented by the following formula. * indicates the bonding position with other atoms.

[0249] [Chemistry 32]

[0250]

[0251] In the formula, R 1 and R 2 Each can be represented independently as a hydrogen atom, alkyl group, or halogen atom.

[0252] In several embodiments, the maleimide compound comprises a compound represented by the following formula (m).

[0253] [Chemistry 33]

[0254]

[0255] In formula (m), X m represents an organic group, and M represents a maleimide group.

[0256] X mThe organic group represented may be a group containing at least one carbon atom, for example, it may be a group containing at least one selected from the group consisting of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups. The organic group may also contain a linking group containing a heteroatom, a substituent containing a heteroatom, etc.

[0257] Maleimide compounds are preferably compounds represented by the following formula (m-1).

[0258] [Chemistry 34]

[0259]

[0260] In equation (m-2), R 1 ~R 4 Each of the following can be used to represent a hydrogen atom, an alkyl group, or a halogen atom, with Y representing a hydrocarbon group.

[0261] R 1 ~R 4 Each and every one of the hydrocarbon groups is preferably a hydrogen atom. The hydrocarbon group represented by Y can have 5 or more carbon atoms, or 10 or more carbon atoms. The hydrocarbon group represented by Y can have 30 or fewer carbon atoms, or 20 or fewer carbon atoms.

[0262] In addition, maleimide compounds can also be synthesized. There are no particular limitations on the methods for synthesizing maleimide compounds. For example, a synthetic method can be listed as follows: using a primary amine and maleic anhydride as raw materials, via maleamic acid or maleamic ester as precursors of maleimide, and cyclizing by dehydration or dealcoholization. The alkyl group of the primary amine can be, for example, a group comprising at least one selected from the group consisting of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups.

[0263] Based on the total mass of the vinylphenyl compound and the maleimide compound, the content of the maleimide compound can be, for example, 10% by mass or more, 15% by mass or more, or 25% by mass or more. When the content of the maleimide compound is 10% by mass or more, the cured product tends to exhibit better heat resistance.

[0264] Furthermore, the content of the maleimide compound can be 90% by mass or less, 85% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. When the content of the maleimide compound is 90% by mass or less, the linear thermal expansion coefficient of the cured material can be kept low.

[0265] From the viewpoint of dielectric properties, curability, and conductor adhesion, the molar ratio of maleimide groups to vinylphenyl groups in the curable composition (maleimide groups / vinylphenyl groups) is preferably 0.05 or more, preferably 0.10 or more, more preferably 0.30 or more, more preferably 0.50 or more, and particularly preferably 0.70 or more.

[0266] Furthermore, from the viewpoint of dielectric properties, curability, and conductor adhesion, the molar ratio (maleimide / vinylphenyl) is preferably 5.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. Additionally, the molar ratio (maleimide / vinylphenyl) may, for example, be 1.0 or less, 0.6 or less, 0.4 or less, or 0.3 or less.

[0267] For the purposes of this study, the molar ratio (maleimide / vinylphenyl) can be 0.05 to 5.0.

[0268] In the curing composition, based on the total amount of specific curing components, the total content of the vinylphenyl compound and the maleimide compound is preferably, for example, 70% to 100% by mass, 80% to 100% by mass, or 90% to 100% by mass. When the total content is 70% by mass or more, the cured product tends to exhibit better heat resistance and a lower coefficient of linear thermal expansion.

[0269] [Inorganic filler material]

[0270] The curable composition of the first embodiment includes at least one inorganic filler selected from the group consisting of titanium oxide, calcium titanate, and strontium titanate (a specific inorganic filler). The specific inorganic filler is an inorganic filler with a relatively high dielectric constant.

[0271] A specific inorganic filler can be used alone or in combination with two or more. For example, specific inorganic fillers with different materials can be used together, or specific inorganic fillers with the same material but different average particle sizes can be used together.

[0272] Specific forms of inorganic fillers include: powder, spherical beads formed from powder, fibers, etc.

[0273] The preferred inorganic filler is calcium titanate. The calcium titanate content in the preferred inorganic filler can be 50% to 100% by mass, 70% to 100% by mass, or 90% to 100% by mass.

[0274] The curable composition of the first embodiment may also contain inorganic fillers other than specific inorganic fillers (also referred to as other inorganic fillers). There are no particular limitations on the types of other inorganic fillers. Examples include fused silica, crystalline silica, and other silica; and inorganic fillers such as alumina, zirconium oxide, glass, talc, clay, mica, barium titanate, and potassium titanate. The inorganic filler may be an inorganic filler with flame-retardant properties. Examples of inorganic fillers with flame-retardant properties include: aluminum hydroxide; magnesium hydroxide; composite metal hydroxides such as magnesium and zinc hydroxides; and zinc borate.

[0275] In the first embodiment, other inorganic fillers may be used alone or in combination with two or more. For example, other inorganic fillers of different materials may be used together, or other inorganic fillers of the same material but different average particle sizes may be used together.

[0276] In the first embodiment, from the viewpoint of reducing the coefficient of linear expansion, other inorganic fillers may include silicon dioxide. From the viewpoint of high thermal conductivity, other inorganic fillers may include alumina. Examples of other inorganic filler forms include: powders, beads formed from powder into spherical shapes, fibers, etc.

[0277] The curable composition of the second embodiment contains an inorganic filler.

[0278] In the second embodiment, the inorganic filler can be used alone or in combination with two or more. For example, inorganic fillers of different materials can be used together, or inorganic fillers of the same material but different average particle sizes can be used together.

[0279] Inorganic fillers can take the form of powder, spherical beads, fibers, etc.

[0280] In the second embodiment, examples of inorganic fillers include fused silica, crystalline silica, etc.; alumina, zirconium oxide, glass, talc, clay, mica, titanium dioxide, calcium titanate, strontium titanate, barium titanate, potassium titanate, etc. The inorganic filler can be an inorganic filler with flame-retardant properties. Examples of inorganic fillers with flame-retardant properties include: aluminum hydroxide; magnesium hydroxide; composite metal hydroxides such as magnesium and zinc hydroxides; zinc borate, etc.

[0281] In the second embodiment, from the viewpoint of reducing the coefficient of linear expansion, the inorganic filler may comprise silicon dioxide. From the viewpoint of high thermal conductivity, the inorganic filler may comprise alumina. From the viewpoint of balancing high dielectric constant and low dielectric loss tangent, the inorganic filler may comprise at least one inorganic filler selected from the group consisting of titanium oxide, calcium titanate, and strontium titanate.

[0282] The average particle size of the inorganic filler is not particularly limited, but is preferably 0.1 μm to 10 μm, and more preferably 0.3 μm to 5 μm. If the average particle size of the inorganic filler is 0.1 μm or more, its dispersibility in the curing component tends to be improved, and the flow characteristics of the curing composition tend to be further improved. If it is 10 μm or less, it tends to be easier to suppress the sedimentation of the inorganic filler, and its permeability and flowability in fine gaps tend to be improved, thereby further suppressing the formation of voids or unfilled portions.

[0283] The average particle size of the inorganic filler can be replaced with the average particle size of a specific inorganic filler or the average particle size of another inorganic filler.

[0284] The average particle size of the inorganic filler can be determined by the following method: Prepare a thin sheet sample from the curing composition or a cured product of the curing composition. Randomly select 100 particles of the inorganic filler from an image obtained using a scanning electron microscope. Measure the major diameter of each particle, and take the arithmetic mean as the average particle size of the inorganic filler.

[0285] In the first embodiment, when the curable composition contains specific inorganic fillers and other inorganic fillers, the content of the specific inorganic filler relative to the total amount of inorganic fillers is not particularly limited. For example, the content of the specific inorganic filler relative to the total amount of inorganic fillers may be 10% to 90% by mass, 20% to 80% by mass, or 30% to 70% by mass. The content of the specific inorganic filler relative to the total amount of inorganic fillers can be appropriately adjusted by considering the balance of dielectric properties, flowability, high thermal conductivity, etc., of the curable composition.

[0286] The content of inorganic filler (which can be replaced by the total content of a specific inorganic filler and other inorganic fillers) may be 25 parts by mass or more, 50 parts by mass or more, or 100 parts by mass or more, relative to the total 100 parts by mass of the curing component. Alternatively, it may be 2000 parts by mass or less, 1500 parts by mass or less, or 1000 parts by mass or less, relative to the total 100 parts by mass of the curing component.

[0287] If the content of inorganic filler is 25 parts by mass or more, the properties of the hardened composition, such as the coefficient of thermal expansion, thermal conductivity, and modulus of elasticity, tend to be further improved. If the content of inorganic filler is 2000 parts by mass or less, the viscosity increase of the hardening composition can be suppressed, and the fluidity can be further improved.

[0288] Based on the mass of the curable composition, the content of inorganic fillers (which can be replaced by the total content of a specific inorganic filler and other inorganic fillers) can be, for example, 20% by mass or more, 35% by mass or more, 40% by mass or more, or 50% by mass or more. Alternatively, the content of inorganic fillers can be 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less.

[0289] Based on the volume of the curable composition, the content of inorganic fillers (which can be replaced by the total content of a specific inorganic filler and other inorganic fillers) can be, for example, 15% by volume or more, 35% by volume or more, 40% by volume or more, 50% by volume or more, or 60% by volume or more. Alternatively, the content of inorganic fillers can be 90% by volume or less, 85% by volume or less, 80% by volume or less, or 75% by volume or less.

[0290] If the content of inorganic filler is 15% by volume or more, the properties of the hardened composition, such as the coefficient of thermal expansion, thermal conductivity, and modulus of elasticity, tend to be further improved. If the content of inorganic filler is 90% by volume or less, the viscosity increase of the hardening composition can be suppressed, and the fluidity can be further improved.

[0291] The hardened material obtained using the hardening composition can be used as a sealant for sealing electronic components such as semiconductor elements.

[0292] [Other ingredients]

[0293] The curing composition may also contain components other than specific curing agents and inorganic fillers. The curing composition may also contain at least one component selected from the group consisting of free radical polymerization initiators and polymerization inhibitors, and may also contain any other arbitrary components. Examples of arbitrary components include coupling agents, release agents, colorants, ion exchangers, flame retardants, stress relievers, and various additives. In addition to the examples below, the curing composition may also contain various additives as needed.

[0294] (Free radical polymerization initiator)

[0295] The curing composition may contain a free radical polymerization initiator. When the curing composition is cured by heating, the free radical polymerization initiator may be a thermal free radical polymerization initiator that generates free radicals upon heating. Examples of thermal free radical polymerization initiators include organic peroxides such as ketal peroxides and dialkyl peroxides, or azo compounds such as azobisbutyronitrile and azobispropionitrile.

[0296] Examples of organic peroxides include: 1,1,3,3-tetramethyl butyl peroxide neodecanoate, di(4-tert-butylcyclohexyl) peroxide dicarbonate, di(2-ethylhexyl) peroxide dicarbonate, cumyl peroxide neodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methyl ethyl peroxide neodecanoate, tert-hexyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-butyl peroxide trimethylacetic acid, 1,1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxide)hexane, tert-hexyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide neoheptanoate, tert-pentyl peroxide-2-ethylhexanoate, di-tert-butyl peroxide hexahydrophthalic acid, and 3,5-dimethyl peroxide-2-ethylhexanoate. 5-Trimethylhexanoate, 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate, tert-pentyl peroxynedecanoate, di(3-methylbenzoyl)peroxide, dibenzoyl peroxide, di(4-methylbenzoyl)peroxide, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di(3-methylbenzoylperoxy)hexane, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxybenzoate, dibutyl peroxytrimethyl adipate, tert-pentyl peroxyoctanoate, tert-pentyl peroxyisononanoate, tert-pentyl peroxybenzoate, etc.

[0297] Examples of azo compounds include: 2,2'-azobis-2,4-dimethylpentanonitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanopentanoic acid), and 1,1'-azobis(1-cyclohexanecarboxylonitrile).

[0298] When the curing composition contains a free radical polymerization initiator, the free radical polymerization initiator may be used alone or in combination with two or more. When the curing composition contains a free radical polymerization initiator, the content of the free radical polymerization initiator may be 0.1% to 30% by mass, 0.1% to 10% by mass, or 0.2% to 3% by mass, based on the total mass of the vinyl phenyl compound and any vinyl compounds other than the vinyl phenyl compound (which may be 0% by mass).

[0299] (Coupling agent)

[0300] The curing composition may contain a coupling agent. When a curing composition contains a coupling agent, there is a tendency for improved adhesion of the cured material or improved adhesion between the curing component and the inorganic filler. Examples of coupling agents include silane coupling agents, titanate coupling agents, aluminum chelate coupling agents, and aluminum / zirconium coupling agents. Silane coupling agents may include, for example, epoxy silane coupling agents, mercapto silane coupling agents, amino silane coupling agents, alkyl silane coupling agents, urea silane coupling agents, vinyl silane coupling agents, (meth)acrylic acid silane coupling agents, and disilazane coupling agents.

[0301] In this disclosure, coupling agents containing vinylphenyl groups are excluded from the scope of said vinylphenyl compounds. That is, vinylphenyl compounds are compounds other than those equivalent to coupling agents.

[0302] Examples of silane coupling agents include: vinyltrichlorosilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl) ) anilinepropyltrimethoxysilane, γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinepropyltriethoxysilane, γ-(N-ethyl)anilinepropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N, N-Dibutylaminopropylmethyldimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.

[0303] When the curing composition contains a coupling agent, the coupling agent may be used alone or in combination with two or more. When the curing composition contains both inorganic filler and coupling agent, the amount is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, relative to 100 parts by weight of the filler. When the coupling agent content is 0.05% by weight or more, there is a tendency for improved adhesion of the cured product.

[0304] (Mold release agent)

[0305] The curing composition may contain a release agent. When the curing composition contains a release agent, it is easy to obtain good release properties from the mold during molding. Examples of release agents include carnauba wax; higher fatty acids such as octacoate and stearic acid, metal salts of higher fatty acids; ester waxes such as octacoate esters; and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.

[0306] When a curing composition contains a release agent, one release agent may be used alone, or two or more may be used in combination. When a curing composition contains a release agent, the release agent content, based on the total mass of the curing components, may be, for example, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more; alternatively, it may be 10% by mass or less, 5% by mass or less, or 2% by mass or less. When the release agent content is 0.01% by mass or more, there is a tendency to obtain sufficient release properties. When the release agent content is 10% by mass or less, there is a tendency to obtain better adhesion.

[0307] (Coloring agent)

[0308] The curable composition may contain a colorant. Examples of known colorants include carbon black, organic dyes, organic pigments, red lead, and iron oxide. The content of the colorant can be appropriately selected according to the intended purpose. The colorant may also function as a filler.

[0309] When the curable composition contains a colorant, the colorant may be used alone or in combination with two or more. When the curable composition contains a colorant, the content of the colorant is, for example, 0.01% to 10% by mass or 0.1% to 5% by mass, based on the total mass of the vinylphenyl compound and the maleimide compound to be included as needed.

[0310] (Polymerization inhibitor)

[0311] The curing composition may contain polymerization inhibitors. Examples of polymerization inhibitors include: phenolic compounds such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and galloquinone; hindered amine compounds, piperidine derivatives, and phenothiazine derivatives.

[0312] (Ion exchanger)

[0313] The curing composition may contain an ion exchanger. When the curing composition contains an ion exchanger, there is a tendency to improve the moisture resistance and high-temperature storage characteristics of electronic components. Examples of ion exchangers include hydrotalcite compounds; hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchanger may also function as a filler. The curing composition may use one type of ion exchanger alone, or two or more types in combination.

[0314] (Flame retardant)

[0315] The curing composition may contain a flame retardant. Examples of flame retardants include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, as well as metal hydroxides. The curing composition may use one flame retardant alone or in combination with two or more.

[0316] (Stress reliever)

[0317] The curing composition may contain a stress reliever. When a curing composition contains a stress reliever, it tends to reduce warping and cracking of electronic components. Examples of stress relievers include: silicone oils; thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers; rubber particles such as natural rubber (NR), acrylonitrile butadiene rubber (NBR), acrylic rubber, urethane rubber, and silicone powder; and rubber particles with a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer (excluding compounds containing vinyl groups within the molecule). When a curing composition contains a stress reliever, one stress reliever may be used alone, or two or more may be used in combination. Commercially available flexibility enhancers may be used as stress relievers.

[0318] [Dielectric properties of the hardened material]

[0319] In several embodiments, the dielectric loss tangent (Df) at 10 GHz when the curing composition is formed into a cured material is, for example, 0.010 or less, 0.0060 or less, 0.0055 or less, or 0.0050 or less. Cured materials with low dielectric loss tangents can suppress the reduction in communication efficiency in electronic devices that use high-frequency radio waves for communication.

[0320] In several embodiments, the relative permittivity (Dk) of the curing composition at 10 GHz when the cured material is formed can be, for example, 5 to 25, 7 to 20, or 10 to 20.

[0321] The hardened material used to determine Df and Dk was a molded object with dimensions of 0.5 mm in length, 0.5 mm in width, and 50 mm in height, obtained by loading the hardening composition into a vacuum hand press and molding it under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 600 seconds, followed by curing at 175°C for 5 hours. The hardened material was then made into test pieces, and the relative permittivity (Dk) and dielectric loss tangent (Df) at 10 GHz were measured using a dielectric constant measuring device (Agilent Technologies, Network Analyzer N5227A) at a temperature of 25°C ± 3°C.

[0322] [Uses of the hardening composition]

[0323] The curable composition disclosed herein is preferably used as a sealing material for electronic component devices that use high-frequency radio waves for communication. Furthermore, the curable composition disclosed herein is preferably used to form dielectric substrates, sealing materials for high-frequency devices, and materials used in parts of high-frequency devices.

[0324] <Electronic Components and Devices>

[0325] In several embodiments, the electronic component device includes, for example, an electronic component and a cured copy of the curable composition of the present disclosure that seals at least a portion of the electronic component. The electronic component device may, for example, be an electronic component module having a plurality of components selected from the group consisting of electronic components and electronic component devices, and a sealing material of the embodiment that seals at least a portion of the plurality of components.

[0326] Examples of electronic components include: active components or parts such as diodes, transistors, integrated circuits, and relays; passive components or parts such as resistors, capacitors, and coils; connectors, support members, terminals, and switches. Examples of electronic component devices include electronic component devices incorporating the aforementioned electronic components; and modules incorporating one or both of the aforementioned electronic components and electronic component devices. Electronic component devices may have support members. Examples of support members include: lead frames, wired carriers, wiring boards, glass, silicon wafers, and organic substrates.

[0327] In particular, in recent years, with the widespread adoption of 5G mobile communication systems, the functionality and miniaturization of semiconductor packaging (PKG) used in electronic components have been driven. Furthermore, the miniaturization and increased functionality of PKGs have also spurred the development of antenna-in-package (AiP) packages, which are PKGs with antenna functions. In AiP, to cope with the increasing number of channels accompanying the diversification of information and the higher frequency of radio waves used in communication, the sealing material must balance high dielectric constant with low dielectric loss tangent.

[0328] In curable compositions, by adjusting the composition of the inorganic filler, a high dielectric constant and a low dielectric loss tangent can be achieved. Therefore, it can also be applied in high-frequency devices to antenna system packages (AiP) that seal antennas mounted on support members using curable compositions.

[0329] For example, one method of manufacturing an electronic component device includes: placing an electronic component on a support member; and sealing at least a portion of the electronic component using a hardening composition disclosed herein. Various forming methods, such as injection molding, transfer molding, and compression molding, can be cited as methods for sealing the electronic component.

[0330] In a method of manufacturing an electronic component device, the hardenable composition disclosed herein can be used to seal at least a portion of the electronic component by injection molding.

[0331] Compared to thermoplastic resins, the curable compositions disclosed herein tend to have a low viscosity during injection molding and are suitable for injection molding at low pressures. Therefore, when sealing electronic components by injection molding, molding can be performed at low pressure and low temperature, and damage to the electronic components can be suppressed.

[0332] In a method for manufacturing an electronic component device, at least a portion of the electronic component can be sealed using the curable composition of the present disclosure by transfer molding, or at least a portion of the electronic component can be sealed using the curable composition of the present disclosure by compression molding.

[0333] For example, another example of a method for manufacturing an electronic component device includes: placing an electronic component on a support member; and sealing at least a portion of the electronic component using a hardening composition disclosed herein and by injection molding.

[0334] Compared to thermoplastic resins, the curable compositions disclosed herein tend to have a low viscosity during injection molding and are suitable for injection molding at low pressures. Therefore, when sealing electronic components by injection molding, molding can be performed at low pressure and low temperature, and damage to the electronic components can be suppressed.

[0335] An example of a manufacturing method for electronic components using an injection molding machine is shown below. Figure 1 middle. Figure 1 The injection molding machine 10 shown includes a mold 1 and an injection unit 3 that supplies a hardening composition into the mold cavity 2 of the mold 1.

[0336] The mold 1 is formed by a movable side mold 1a and a fixed side mold 1b. With a support member (not shown) containing electronic components disposed in the mold cavity 2 of the mold 1, a hardening composition is supplied from the nozzle 6 of the injection machine 3.

[0337] The injection molding machine 3 includes: a hopper 4, a supply section for supplying the components of the hardening composition; a barrel 5, which uses a screw or the like to agitate the mixture of components supplied from the hopper 4; and a nozzle 6, disposed on the upstream side of the barrel 5. The injection molding machine 3 is not limited to injecting a filled, molten, hardening composition into the mold cavity 2. Figure 1 The structure shown.

[0338] like Figure 1 As indicated by arrow A in (a), the components of the hardening composition are supplied from hopper 4 to cylinder 5. As... Figure 1 As shown in (b), a hardening composition is prepared by heating and stirring the mixture of components inside barrel 5. The heating temperature of the hardening composition inside barrel 5 can be within the range where a hardening reaction does not occur, for example, it can be 50℃~100℃, 60℃~80℃, or around 70℃. When stirring the mixture using a screw, the screw speed can be, for example, 30 rpm (revolutions per minute)~100 rpm, 40 rpm~80 rpm, or around 50 rpm.

[0339] like Figure 1As shown in (c), the hardening composition prepared is supplied from nozzle 6 into mold cavity 2 of mold 1 to barrel 5 at a specified injection pressure, injection speed, and injection time. The injection pressure can be, for example, 1 MPa to 10 MPa, 2 MPa to 8 MPa, or approximately 5 MPa. The injection speed can be 0.5 cm. 3 / sec~10 cm 3 / sec, or 1 cm 3 / sec~8cm 3 / sec, or 5 cm 3 The emission time can be approximately 30 to 300 seconds, 50 to 200 seconds, or around 140 seconds.

[0340] The heating temperature of the hardening composition in the mold cavity 2 (also known as temperature T1 (unit °C)) is preferably higher than the heating temperature of the hardening composition in the barrel 5 (also known as temperature T2 (unit °C)). For example, it can satisfy T1≧T2+40, T2+50≦T1≦150, or T2+80≦T1≦130. The heating time of the hardening composition in the mold cavity 2 can be 30 seconds to 300 seconds, 50 seconds to 200 seconds, or about 140 seconds.

[0341] After heating the curable composition within the mold cavity 2, the fixed-side mold 1b and the movable-side mold 1a are opened, and the molded article is removed from the mold 1. Then, as needed, the molded article is post-cured at 150°C to 200°C for a curing time of 30 minutes to 10 hours (e.g., 175°C for 6 hours). This allows for the acquisition of an electronic component device in which at least a portion of the electronic component is sealed with a cured product of the curable composition disclosed herein.

[0342] <High-Frequency Device>

[0343] The high-frequency device disclosed herein comprises a cured form of the curing composition of the present disclosure. Examples of high-frequency devices include, for example, microstrip antennas, dielectric waveguides, and multilayer antennas.

[0344] <Dielectric substrate>

[0345] The dielectric substrate of this disclosure is formed by curing the curable composition of this disclosure. For example, the dielectric substrate of this disclosure can be used to form the microstrip antenna described later.

[0346] <Microstrip Antenna>

[0347] The microstrip antenna disclosed herein includes: a dielectric substrate formed by curing the curable composition of the present disclosure; a radiating element disposed on one side of the dielectric substrate; and a ground conductor plate disposed on the other side of the dielectric substrate.

[0348] The radiating element is preferably a component comprising any one of a metallic material, an alloy of a metallic material, a hardened metal paste, or a conductive polymer. Examples of the shape of the radiating element include rectangles and circles.

[0349] The microstrip antenna includes a radiating element with a length L and a width W, and preferably resonates at a frequency that is an integer multiple of L and half the wavelength.

[0350] The ground conductor plate is a plate-shaped component containing highly conductive metals such as copper, silver, and gold. The thickness of the ground conductor plate is preferably sufficiently thin relative to the center operating frequency of the antenna device, for example, preferably about one-fiftieth to one-thousandth of the wavelength of the center operating frequency.

[0351] <Dielectric Waveguide>

[0352] The dielectric waveguide comprises: a dielectric material formed by curing the curable composition of the present disclosure; and a conductive film covering the surface of the dielectric material. The dielectric waveguide confines and transmits electromagnetic waves within the dielectric material.

[0353] The conductor film contains metals such as copper, oxide high-temperature superconductors, etc.

[0354] <Multi-layer antenna>

[0355] The multilayer antenna includes: a dielectric material formed by curing the hardening composition disclosed herein; and a circuit disposed on the dielectric material and having a structure in which the dielectric material and the circuit are stacked.

[0356] As components in a circuit, examples include capacitors and inductors. Dielectrics can be sheet-like components (dielectric sheets).

[0357] For example, a multilayer antenna can be formed by stacking dielectric sheets printed with circuits including components such as capacitors and inductors.

[0358] Example

[0359] The embodiments of this disclosure are described in detail through examples. The embodiments of this disclosure are not limited to the following examples.

[0360] <Synthesis of Vinylphenyl Compounds>

[0361] In a 500 mL reaction vessel including a stirrer, thermometer, reflux tube, and nitrogen inlet, 35.6 parts by mass of indene, 99.1 parts by mass of chloromethylstyrene, 7.1 parts by mass of tetrabutylammonium bromide as a phase transfer catalyst, 0.1 parts by mass of phenothiazine as a polymerization inhibitor, and 76.4 parts by mass of toluene as a solvent were added. The resulting composition was stirred at 40 °C while nitrogen was purged at a flow rate of 50 mL / min.

[0362] In addition, as chloromethylstyrene, a mixture of o-chloromethylstyrene and p-chloromethylstyrene was used (Wujin Linchuan Chemical Co., Ltd., with o-chloromethylstyrene content of 17% by mass and p-chloromethylstyrene content of 83% by mass).

[0363] Subsequently, 46.5 parts by mass of an aqueous sodium hydroxide solution (48% by mass) as an alkaline compound were added dropwise over 20 minutes, followed by stirring at 60°C for 9 hours. Nitrogen gas was continuously purged during the reaction. The composition was cooled to room temperature (25°C), neutralized with a 10% by mass hydrochloric acid solution, and then washed twice with pure water. Afterward, toluene was removed by vacuum distillation, the resulting viscous liquid was washed with methanol, and then dried under vacuum to obtain the vinylphenyl compound.

[0364] Vinylphenyl compounds via 1 H-NMR ( 1 H-Nuclear Magnetic Resonance, 1 ¹H NMR analysis confirmed that the two hydrogen atoms directly bonded to the carbon atom at position 1 of indene were substantially entirely replaced by vinylbenzyl groups (vinylphenylmethyl). Furthermore, GPC analysis confirmed that the vinylphenyl compound was a mixture of compounds with two and three vinylbenzyl groups, with an average number of vinylbenzyl groups ranging from 1.8 to 2.6. The weight-average molecular weight (Mw) of the vinylphenyl compound was 500.

[0365] [Chemistry 35]

[0366]

[0367] In the examples, the weight-average molecular weight (Mw) was calculated by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve was approximated using standard polystyrene: TSK standard polystyrene (Type: A-2500, A-5000, F-20, F-80) (Tosoh Corporation) in cubic form.

[0368] Equipment: High-speed GPC device HLC-8320GPC (Tosoh Corporation)

[0369] Detector: UV-8320 ultraviolet absorbance detector (Tosoh Corporation)

[0370] Columns: Guard column: TSK Gel Guard Column Super (HZ)-M+; Gel Super Multipore HZ-M (two columns); Reference column: TSK Gel Super H-RC (two columns) (All from Tosoh Corporation)

[0371] Tubing string dimensions: 4.6 mm × 20 mm (protective tubing string), 4.6 mm × 150 mm (tubing string), 6.0 mm × 150 mm (reference tubing string)

[0372] Eluent: Tetrahydrofuran

[0373] Sample concentration: 10 mg / 1 mL

[0374] Injection volume: 20 μL or 2 μL

[0375] Flow rate: 0.35 mL / min

[0376] Measurement temperature: 40℃

[0377] <Preparation of the Hardening Composition>

[0378] The obtained vinylphenyl compounds were placed in metal tanks and allowed to stand for 5 hours in a vacuum dryer at a pressure below 0.1 MPa and a temperature of 70°C to remove the solvent.

[0379] [Examples 1A to 4A and Comparative Example 1A]

[0380] The solvent-removed vinylphenyl compound 1 was mixed with the components listed in Table 1 to prepare a solid, curable composition. In each embodiment, the molar ratio of maleimide to vinylphenyl (maleimide / vinylphenyl) was 1.0.

[0381] [Example 5A]

[0382] A solid vinylphenyl compound 2 (resin (I)) synthesized as follows was mixed with the components listed in Table 1 to prepare a solid curable composition. In Example 5A, the molar ratio of maleimide to vinylphenyl (maleimide / vinylphenyl) was 1.0.

[0383] -Synthesis of Resin (I)-

[0384] In a reaction vessel including a stirrer, thermometer, reflux pipe, and nitrogen inlet, 116.16 parts by mass of indene, 113.78 parts by mass of p-xylene dichloride, 15.5 parts by mass of tetrabutylammonium bromide (manufactured by Kanto Chemical Co., Ltd.), 0.90 parts by mass of phenothiazine, and 700 parts by mass of toluene were charged. The mixture was heated and stirred at 40°C while nitrogen was purged at a flow rate of 50 ml / min. Then, 369 parts by mass of a sodium hydroxide aqueous solution (48% by mass) was added, and the temperature was raised to 70°C. Stirring was continued, and after the reaction of p-xylene dichloride was confirmed by nuclear magnetic resonance (NMR), 122.10 parts by mass of chloromethylstyrene was added. The reaction was then carried out at 70°C, and the reaction was concluded after NMR confirmation. The reaction mixture was cooled to room temperature (25°C), neutralized with a 10% hydrochloric acid aqueous solution, and washed twice with pure water. After removing toluene by vacuum distillation, the resulting viscous liquid is washed with methanol and then dried under vacuum to obtain resin (I).

[0385] The number-average molecular weight (Mn) of resin (I) is 611, and the weight-average molecular weight (Mw) is 839. In the graphs obtained from High Performance Liquid Chromatography (HPLC) analysis under the following conditions, the combined area of ​​the four peaks detected during the period of 32 to 35 minutes was 52.44% of the total area. Furthermore, based on Liquid Chromatography-Mass Spectrometry (LC-MS) analysis, compounds represented by the following structural formulas were presumed to have been generated.

[0386] (Conditions for high performance liquid chromatography (HPLC) analysis)

[0387] Sample: 0.0001% by mass tetrahydrofuran solution of resin

[0388] Injection volume: 20 μL

[0389] Mobile phase: Tetrahydrofuran

[0390] Flow rate: 0.8 ml / min

[0391] Degasser: "DEGAS" (manufactured and traded by Resonac Inc.)

[0392] Pump: "DS-4" (manufactured by Resonac Inc., trade name)

[0393] Tube Column: "SHODEX KF-802+KF-801"×3 (manufactured by Resonac Co., Ltd., trade name)

[0394] Column temperature: 40℃

[0395] Column oven: "AO-50" (manufactured by Resonac Inc., trade name)

[0396] Detector: Ultraviolet absorbance detector (UV-41 manufactured by Resonac Inc., measurement wavelength 254 nm)

[0397] [Chemistry 36]

[0398]

[0399] [Example 1B]

[0400] The solvent-removed vinylphenyl compound was mixed with the components listed in Table 2 to prepare a solid, curable composition. The molar ratio of maleimide to vinylphenyl (maleimide / vinylphenyl) was 3.3.

[0401] The components listed in Tables 1 and 2 are as follows. In Tables 1 and 2, the unit for each component is "parts by mass". The average particle size of the inorganic filler was determined by the method described herein.

[0402] Vinylphenyl compound 1: The obtained vinylphenyl compound (vinyl benzyl compound) is a liquid at room temperature.

[0403] Vinylphenyl compound 2: The obtained vinylphenyl compound (vinyl benzyl compound, resin (I)) is a solid at room temperature.

[0404] Maleimide compound: 4,4'-bismaleimide diphenylmethane, solid at room temperature.

[0405] • Epoxy Resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq

[0406] • Epoxy Resin 2: Biphenyl-type epoxy resin, epoxy equivalent 192 g / eq

[0407] • Hardener 1: Biphenyl aryl phenolic resin, hydroxyl equivalent 199 g / eq

[0408] • Hardener 2: Active ester compound 1: DIC Corporation, product name "EXB-8"

[0409] • Hardening accelerator: Triphenylphosphine / 1,4-benzoquinone adduct

[0410] Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., product name "KBM-573")

[0411] Coupling agent 2: 3-Mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., product name "KBM-803")

[0412] Release agent 1: α-olefin / maleic anhydride copolymer

[0413] Release agent 2: Octadecate wax (Clariant Japan Co., Ltd., product name "HW-E")

[0414] Release agent 3: Oxidized polyethylene wax

[0415] • Colorant 1: Carbon Black (Mitsubishi Chemical Corporation, product name "MA600")

[0416] • Colorant 2: Carbon black (Mitsubishi Chemical Corporation, product name "MA100RMJ")

[0417] • Additives: Piperidine derivatives

[0418] Inorganic filler 1: Alumina, average particle size 7 μm

[0419] Inorganic filler 2: Calcium titanate, average particle size 0.2 μm

[0420] Inorganic filler 3: Calcium titanate, average particle size 6 μm

[0421] Inorganic filler 4: Calcium titanate, average particle size 20 μm

[0422] Inorganic filler 5: Silica filler, average particle size 18 μm

[0423] <Production of Hardened Materials>

[0424] Cured materials were prepared using a curing composition, and the properties shown in Tables 1 and 2 were measured. The results are presented in Tables 1 and 2.

[0425] (Determination of dielectric properties (Df and Dk))

[0426] The curing composition was loaded into a vacuum hand press and shaped under conditions of mold temperature 175°C, forming pressure 6.9 MPa, and curing time 600 seconds. After curing at 175°C for 5 hours, a cured material with dimensions of 0.5 mm in length, 0.5 mm in width, and 50 mm in height was obtained. The cured material was made into test pieces, and the relative permittivity (Dk) and dielectric loss tangent (Df) at 10 GHz were measured using a dielectric constant measuring device (Agilent Technologies, Network Analyzer N5227A) at a temperature of 25°C ± 3°C.

[0427] (Determination of gelation time)

[0428] The gel time (seconds) was determined by measuring the time from when 0.5 g (Examples 1A to 5A and Comparative Example 1A) or 0.7 g (Example 1B) of the curing composition was placed on a heating plate preheated to 175°C until the resin lost its tackiness.

[0429] (Molding shrinkage rate)

[0430] The molding shrinkage rate was determined according to JIS K6911. Using a transfer molding machine, the hardening composition was molded at a molding temperature of 175°C, a molding pressure of 6.9 MPa, and a hardening time of 120 seconds to obtain a disc-shaped molded article (90 mm in diameter, 11 mm in thickness, and 80 mm in outer diameter of the protruding annular portion) with a raised annular portion. The molded article was then hardened at 175°C for 5 hours to obtain a cured product.

[0431] Based on the pre-measured outer diameter length D of the mold ring at 25°C and the outer diameter length d of the protruding ring of the hardened material at room temperature (25°C), the molding shrinkage rate (%) is calculated using the following formula.

[0432] Molding shrinkage rate (%) = ((Dd) / D) × 100

[0433] (Determination of linear expansion rate)

[0434] The product was manufactured as follows: The curable composition was formed using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, followed by post-curing at 175°C for 5 hours. The cured product was a rectangle with a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm. The linear expansion coefficients α1 (ppm / °C) and α2 (ppm / °C) were measured using a thermomechanical analysis device (e.g., a TMA / SS6100 manufactured by Seiko Instruments Co., Ltd.). Furthermore, the test load was set to 98 mN, and the heating rate was set to 5°C / min.

[0435] (Glass transition temperature (Tg) of the hardened material)

[0436] Regarding Examples 1A to 5A and Comparative Example 1A, the temperature at the intersection of the tangent at 20°C to 40°C and the tangent at 220°C to 260°C, obtained by measuring the linear expansion rate, is set as the glass transition temperature (°C) of the hardened material.

[0437] Regarding Example 1B, the temperature at the intersection of the tangent at 10°C to 30°C obtained by measuring the linear expansion rate and the tangent at 200°C to 220°C is set as the glass transition temperature (°C) of the hardened material.

[0438] (Spiral flow)

[0439] In the determination of spiral flow, the flow distance (cm) when the curable composition is molded under the conditions of mold temperature 175°C, molding pressure 6.9 MPa and curing time 90 seconds is determined using a spiral flow test mold according to the Epoxy Molding Material Institute (EMMI)-1-66.

[0440] (Comment on rough edges)

[0441] The curing composition was loaded into a transfer molding machine and molded at a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds. After molding, the length of the longest flow of the curing composition in the 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, and 2 μm slits created in the mold was measured using vernier calipers, and the measured value was set as the burr length (mm).

[0442] (Hardness at heat)

[0443] The hardening composition was loaded into a transfer molding machine and formed into a circular plate with a diameter of 50 mm and a thickness of 3 mm under the conditions of mold temperature of 180°C, molding pressure of 6.9 MPa and hardening time of 90 seconds. Immediately after forming, the hardness was measured using a Shore D hardness tester (Uejima Manufacturing Co., Ltd., HD-1120 (Type D)).

[0444] (Melt viscosity (ηFT))

[0445] A flow tester was used to determine the melt viscosity (Poise) of a hardening composition heated to 175°C.

[0446] (Determination of flexural modulus of elasticity, flexural strength and flexural elongation at break)

[0447] The curing composition was loaded into a transfer molding machine and molded at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds. It was then post-cured at 175°C for 6 hours to produce a cuboid test piece with a shape of 127 mm × 12.7 mm × 4 mm.

[0448] Using a Tensilon (A&D) instrument as the evaluation device, a three-point support bending test according to JIS-K-7171 (2016) was conducted at room temperature (25°C), and the flexural modulus E, flexural strength S, and flexural elongation at break ε of the test specimen were determined by the following formula.

[0449] The flexural modulus of elasticity E (GPa), flexural strength S (MPa), and flexural elongation at break ε (%) can be defined by the following formulas.

[0450] In the following formula, P is the force gauge value (N), y is the displacement (mm), l is the span = 64 mm, w is the test piece width = 12.7 mm, and h is the test piece thickness = 4 mm. The subscript max indicates the maximum value.

[0451] [Formula 1]

[0452]

[0453] [Formula 2]

[0454]

[0455] [Formula 3]

[0456]

[0457] (Water absorption rate)

[0458] The curing composition was loaded into a vacuum hand press and formed under conditions of mold temperature 175°C, forming pressure 6.9 MPa, and curing time 600 seconds. After curing at 180°C for 6 hours, a plate-shaped cured material (12.5 mm long, 25 mm wide, and 0.2 mm thick) was obtained. The freshly manufactured plate-shaped cured material was then placed in a pressure cooker at 121°C / 2.1 atm and removed after 24 hours. The increase in mass relative to the initial mass was calculated (%).

[0459] Water absorption rate (mass%) = [(mass after input - mass before input) / mass before input] × 100

[0460] (Circular plate flow)

[0461] Using a flat die for measuring circular plate flow, with an upper die of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower die of 200 mm (W) × 200 mm (D) × 15 mm (H), 5 g of a curing composition weighed using a pan balance was placed in the center of the lower die heated to 180°C. After 5 seconds, the upper die heated to 180°C was closed, and compression molding was performed under a load of 78 N and a curing time of 90 seconds. The major diameter (mm) and minor diameter (mm) of the molded product were measured using vernier calipers, and their average value (mm) was taken as the circular plate flow.

[0462] [Table 1]

[0463]

[0464] [Table 2]

[0465]

[0466] As shown in Table 1, the dielectric loss tangent was suppressed lower in Examples 1A to 5A containing vinylphenyl and maleimide compounds compared to Comparative Example 1A which did not contain vinylphenyl and maleimide compounds. Furthermore, in Example 5A using a solid vinylphenyl compound, the dielectric loss tangent was suppressed even lower compared to Comparative Example 1A.

[0467] Furthermore, in Examples 1A to 5A, compared to Comparative Example 1A, a hardened material with low molding shrinkage and high heat resistance was obtained.

[0468] As shown in Table 2, it was confirmed that the hardening composition prepared in Example 1B has excellent flowability and can be used for injection molding.

[0469] The entire contents of the disclosures of Japanese Patent Application Nos. 2024-057285 and 2024-057286, filed on March 29, 2024, are incorporated herein by reference.

[0470] All documents, patent applications and technical specifications set forth in this specification are incorporated herein by reference to the same extent that each document, patent application and technical specification is specifically described and incorporated herein by reference.

Claims

1. A hardening composition comprising: Hardening components containing ethylene-like unsaturated double bonds and capable of free radical polymerization; and At least one inorganic filler selected from the group consisting of titanium oxide, calcium titanate and strontium titanate.

2. A hardening composition for injection molding and comprising: Hardening components containing ethylene unsaturated double bonds and capable of free radical polymerization, and Inorganic filler material.

3. The hardening composition according to claim 1 or 2, wherein, The curing component comprises at least one compound selected from the group consisting of compounds having a vinylphenyl group and compounds having a maleimide group.

4. The hardening composition according to any one of claims 1 to 3, wherein, The curing component comprises a vinylphenyl compound that is liquid at 25°C and a maleimide compound that is solid at 25°C.

5. The hardening composition according to any one of claims 1 to 4, wherein, The curing component comprises a compound having a vinylphenyl group and a compound having a maleimide group, wherein the molar ratio of maleimide group to vinylphenyl group (maleimide group / vinylphenyl group) is 0.05 to 5.

0.

6. The curing composition according to any one of claims 1 to 5, wherein it is a solid at 25°C.

7. The hardening composition according to any one of claims 1 to 6, wherein, The curing component comprises a compound having a vinylphenyl group, wherein the compound having a vinylphenyl group comprises a compound represented by the following formula (b1); [Chemistry 1] (where X) b1 B represents an organic group, B represents a group containing vinylphenyl groups independently, and l represents an integer from 1 to 5.

8. The hardening composition according to any one of claims 1 to 7, wherein, The curing component comprises a compound having vinylphenyl groups, wherein the compound having vinylphenyl groups comprises a compound having two or more vinylphenyl groups.

9. The hardening composition according to any one of claims 1 to 8, wherein, The curing component comprises a compound having a vinylphenyl group, wherein the compound having a vinylphenyl group comprises a compound represented by the following formula (b3); [Chemistry 2] (In the formula, B) hb Each of the following formulas (Bz) independently represents a hydrogen atom or a group, with at least one B. hb The group represented by the following formula (Bz); [Chemistry 3] (In the formula, * indicates the location of the bond).

10. The hardening composition according to any one of claims 1 to 9, wherein, The curing component comprises a compound having a vinylphenyl group, and the compound having a vinylphenyl group comprises a polymer having a vinylphenyl group.

11. The hardening composition according to any one of claims 1 to 10, wherein, The curing component comprises a compound having a vinylphenyl group, wherein the compound having a vinylphenyl group comprises a polymer having a structural unit represented by the following formula (Bb); [Chemistry 4] (In the formula, X represents an organic group, B represents a group containing vinylphenyl independently, R represents a substituent independently, l represents an integer from 1 to 5, m represents an integer from 0 to 10; * represents the bond position with other atoms).

12. The hardening composition according to any one of claims 1 to 11, wherein, The curing component comprises a compound having a vinylphenyl group, which comprises at least one selected from the group consisting of polymers represented by formula (B3-3) and polymers represented by formula (B3-7). [Chemistry 5] (In the formula, B) b Each group represented by the following formula (Bz) can be independently represented, where n represents a number from 3 to 5; the benzene ring can have substituents at the positions where substitution is possible; [Chemistry 6] (In the formula, B) b Each group represented by the following formula (Bz) can be independently represented, where n represents a number from 3 to 5; the benzene ring can have substituents at the positions where substitution is possible; [Chemistry 7] (In the formula, * indicates the location of the bond).

13. The hardening composition according to any one of claims 1 to 12, wherein, The curing component comprises a compound having a vinyl benzyl group, wherein the compound having a vinyl benzyl group comprises a compound represented by the following formula (A); [Chemistry 8] (In the formula, R) 1 Each R is an independent monovalent organic group, halogen atom, hydrogen atom, or bond position with other structures. 1 At least one of them is vinylbenzyl, R 4 R can be independently a monovalent organic group, a halogen atom, a hydrogen atom, or a bond position with other structures. x1 and R x2 Each is independently a divalent aliphatic hydrocarbon group or a single bond, Ar is a substituted or unsubstituted biphenylene, or a substituted or unsubstituted biphenylene, and n is an integer greater than or equal to 1.

14. The hardening composition according to any one of claims 1 to 13, wherein, The dielectric loss tangent of the cured material at 175℃ for 6 hours is below 0.

010.

15. The curing composition according to any one of claims 1 to 14, used to form a part of a high-frequency device.

16. An electronic component device having an electronic component and a cured product of a curable composition according to any one of claims 1 to 15 sealing at least a portion of the electronic component.

17. A high-frequency device having a hardened form of the hardening composition according to any one of claims 1 to 15.

18. A dielectric substrate formed by curing a curable composition according to any one of claims 1 to 15.

19. A microstrip antenna, comprising: The dielectric substrate according to claim 18; A radiating element is disposed on one side of the dielectric substrate; and A ground conductor plate is disposed on the other side of the dielectric substrate.

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