Resin composition for molding and electronic component device

Abstract

A resin composition for molding containing: an epoxy resin; a curing agent that contains an active ester compound; an inorganic filler; and porous polymer particles.

Description

Molding resin composition and electronic component device

[0001] The present disclosure relates to a molding resin composition and an electronic component device.

[0002] In recent years, with the demand for electronic devices to be more highly functional and lighter, thinner, shorter, and smaller, the integration and even higher density of electronic components have progressed, and the semiconductor packages used in these electronic devices have become smaller than ever before.Furthermore, the radio waves used for communication in electronic devices have become higher in frequency.

[0003] For example, Patent Documents 1 and 2 propose high-dielectric resin compositions for use in sealing semiconductor elements, from the viewpoint of miniaturizing semiconductor packages and adapting to high frequencies.

[0004] JP 2015-036410 A JP 2018-141052 A

[0005] Examples of materials for encapsulating electronic components such as semiconductor devices include molding resin compositions containing an epoxy resin, a curing agent, and an inorganic filler. When a material with a high dielectric loss tangent is used as the molding resin composition, the transmission signal is converted into heat due to dielectric loss, which tends to reduce communication efficiency. The amount of dielectric loss generated when radio waves transmitted for communication are converted into heat in a dielectric is expressed as the product of the square root of the frequency, the dielectric constant, and the dielectric loss tangent. Transmission signals are more likely to be converted into heat in proportion to their frequency. In particular, in recent years, radio waves used for communication have become higher in frequency to accommodate the increasing number of channels associated with the diversification of information. To suppress dielectric loss, molding resin compositions capable of molding cured products with a low dielectric constant are needed.

[0006] The present disclosure has been made in consideration of the above-described conventional circumstances, and an object of the present disclosure is to provide a molding resin composition that can be molded into a cured product having a low relative dielectric constant, and an electronic component device using the same.

[0007] Specific means for achieving the above object are as follows. <1> A molding resin composition comprising an epoxy resin, a curing agent containing an active ester compound, an inorganic filler, and porous polymer particles. <2> The molding resin composition according to <1>, wherein the porous polymer particles have a core having a porous shape and a shell covering at least a portion of the core. <3> The molding resin composition according to <1> or <2>, wherein the porous polymer particles have a core having a porous shape, the core comprising at least one polymer selected from the group consisting of a (meth)acrylic polymer, an olefin polymer, a styrene polymer, and a urethane polymer. <4> The molding resin composition according to any one of <1> to <3>, wherein the content of the porous polymer particles is 5% to 50% by volume based on the total amount of the inorganic filler and the porous polymer particles. <5> The molding resin composition according to any one of <1> to <4>, wherein the content of the porous polymer particles is 3% to 40% by volume based on the total amount of the molding resin composition. <6> The molding resin composition according to any one of <1> to <5>, wherein the porous polymer particles are thermosetting. <7> The molding resin composition according to any one of <1> to <6>, which is used for a high-frequency device. <8> The molding resin composition according to <7>, which is used for encapsulating an electronic component in a high-frequency device. <9> The molding resin composition according to <7>, which is used for an antenna-in-package. <10> An electronic component device comprising: a support member; an electronic component placed on the support member; and a cured product of the molding resin composition according to any one of <1> to <9> encapsulating the electronic component. <11> The electronic component device according to <10>, wherein the electronic component includes an antenna.

[0008] According to the present disclosure, it is possible to provide a molding resin composition that can be molded into a cured product having a low relative dielectric constant, and an electronic component device using the same.

[0009] Fig. 1 is a graph showing the SS curves of the elongation at break and flexural strength obtained using the molding resin compositions of each Example and Comparative Example. Fig. 2 is a graph showing the change in viscoelastic properties obtained using a composition containing Filler 5.

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0011] In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, particles corresponding to each component may contain multiple types of particles. When multiple types of particles corresponding to each component are present in a composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0012] <Molding Resin Composition> The molding resin composition of the present disclosure includes an epoxy resin, a curing agent including an active ester compound, an inorganic filler, and porous polymer particles, and is thereby capable of molding a cured product having a low dielectric constant.

[0013] The components constituting the molding resin composition will be described below. The molding resin composition of the present disclosure contains at least an epoxy resin, a curing agent, an inorganic filler, and porous polymer particles, and may contain other components as necessary.

[0014] (Epoxy Resin) The molding resin composition of the present disclosure contains an epoxy resin. The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule. The mass proportion of the epoxy resin in the entire molding resin composition is preferably 0.5% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, and even more preferably 3.5% by mass to 13% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, etc.

[0015] Examples of epoxy resins include novolac epoxy resins (phenol novolac epoxy resins, o-cresol novolac epoxy resins, etc.) obtained by epoxidizing a novolac resin obtained by condensing or co-condensing, under an acidic catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde; triphenylmethane epoxy resins obtained by epoxidizing a triphenylmethane phenolic resin obtained by condensing or co-condensing, under an acidic catalyst, the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde; and triphenylmethane epoxy resins obtained by epoxidizing a triphenylmethane phenolic resin obtained by condensing or co-condensing, under an acidic catalyst, the above-mentioned phenolic compound, naphthol compound, and an aldehyde compound. diphenylmethane-type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, or the like; biphenyl-type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins in which active hydrogen bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, or the like is substituted with a glycidyl group; and dicyclopentadiene-type epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenolic compound.Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are obtained by epoxidizing an intramolecular olefin bond; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include dicyclopentadiene-modified epoxy resins, which are glycidyl ethers of cyclopentadiene-modified phenolic resins, polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins, naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins, halogenated phenol novolac-type epoxy resins, hydroquinone-type epoxy resins, trimethylolpropane-type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Epoxidized acrylic resins are also suitable as epoxy resins. The epoxy resins may be used alone or in combination of two or more.

[0016] The epoxy resin may contain at least one of a triphenylmethane type epoxy resin, an o-cresol novolac type epoxy resin, a biphenyl aralkyl type epoxy resin, and a biphenyl type epoxy resin, or may contain a triphenylmethane type epoxy resin and a biphenyl type epoxy resin, or a triphenylmethane type epoxy resin and an o-cresol novolac type epoxy resin.

[0017] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq. The epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.

[0018] When the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. The softening point or melting point of the epoxy resin is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of handleability during preparation of the molding resin composition. The melting point or softening point of the epoxy resin is a value measured by differential scanning calorimetry (DSC) or a method in accordance with JIS K 7234:1986 (ring and ball method).

[0019] (Curing Agent) The molding resin composition of the present disclosure includes a curing agent containing an active ester compound. The molding resin composition may include only one type of curing agent, or may include two or more types of curing agents. For example, the curing agent may include only one type of active ester compound, or may include two or more types of active ester compounds, or may include an active ester compound and another curing agent (e.g., a phenolic curing agent).

[0020] When a phenolic curing agent is used as an epoxy resin curing agent, for example, secondary hydroxyl groups are generated in the reaction between the epoxy resin and the phenolic curing agent. In contrast, when an active ester compound is used as an epoxy resin curing agent, ester groups are generated instead of secondary hydroxyl groups in the reaction between the epoxy resin and the active ester compound. Because ester groups have lower polarity than secondary hydroxyl groups, it is presumed that molding resin compositions containing an active ester compound as a curing agent can reduce the dielectric tangent and relative dielectric constant of the cured product compared to molding resin compositions containing only a curing agent that generates secondary hydroxyl groups. Furthermore, while polar groups in a cured product increase the water absorption of the cured product, using an active ester compound as a curing agent can reduce the concentration of polar groups in the cured product, thereby suppressing the water absorption of the cured product. Furthermore, suppressing the water absorption of the cured product, in other words, reducing the polar molecule H ２ It is presumed that by reducing the O content, the dielectric loss tangent and relative dielectric constant of the cured product can be further reduced.

[0021] - Active Ester Compound - Here, the active ester compound refers to a compound that has one or more ester groups in one molecule that react with epoxy groups and has the ability to harden epoxy resins.

[0022] The type of active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with an epoxy group. Examples of active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds. These active ester compounds may be used alone or in combination of two or more.

[0023] Examples of active ester compounds include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds using an aliphatic compound as a polycondensation component tend to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain. Ester compounds using an aromatic compound as a polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring.

[0024] Specific examples of active ester compounds include aromatic esters obtained by the condensation reaction of an aromatic carboxylic acid with a phenolic hydroxyl group. Among these, aromatic esters obtained by the condensation reaction of an aromatic carboxylic acid with a phenolic hydroxyl group using a mixture of raw materials: an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms on the aromatic ring of benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfonic acid, etc. are substituted with carboxy groups; a monohydric phenol in which one hydrogen atom on the aromatic ring is substituted with a hydroxyl group; and a polyhydric phenol in which 2 to 4 hydrogen atoms on the aromatic ring are substituted with hydroxyl groups. That is, aromatic esters having structural units derived from the aromatic carboxylic acid component, structural units derived from the monohydric phenol, and structural units derived from the polyhydric phenol are preferred.

[0025] Specific examples of the active ester compound include an active ester resin having a structure obtained by reacting a phenolic resin having a molecular structure in which phenolic compounds are bonded via alicyclic hydrocarbon groups with an aromatic dicarboxylic acid or a halide thereof, and an aromatic monohydroxy compound, as described in JP 2012-246367 A. As the active ester resin, a compound represented by the following structural formula (1) is preferred.

[0026]

[0027] In structural formula (1), R １represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; X represents an unsubstituted benzene ring, an unsubstituted naphthalene ring, a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; Y represents a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms; k is 0 or 1; and n represents the average number of repetitions and is 0 to 5.

[0028] Specific examples of the compound represented by structural formula (1) include the following exemplary compounds (1-1) to (1-10): In the structural formula, t-Bu is a tert-butyl group.

[0029]

[0030]

[0031] Other specific examples of the active ester compound include a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3), which are described in JP 2014-114352 A.

[0032]

[0033] In structural formula (2), R １ and R ２ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Z is an ester-forming structural moiety (z1) selected from the group consisting of an unsubstituted benzoyl group, an unsubstituted naphthoyl group, a benzoyl group or naphthoyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2); and at least one of Z is an ester-forming structural moiety (z1).

[0034] In structural formula (3), R １ and R ２are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Z is an ester-forming structural moiety (z1) selected from the group consisting of an unsubstituted benzoyl group, an unsubstituted naphthoyl group, a benzoyl group or a naphthoyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2); and at least one of Z is an ester-forming structural moiety (z1).

[0035] Specific examples of the compound represented by structural formula (2) include the following exemplary compounds (2-1) to (2-6).

[0036]

[0037] Specific examples of the compound represented by structural formula (3) include the following exemplary compounds (3-1) to (3-6).

[0038]

[0039] Commercially available products may be used as the active ester compound. Examples of commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK", "EXB-8", and "EXB-9425" (manufactured by DIC Corporation) as active ester compounds containing an aromatic structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac.

[0040] The ester equivalent (molecular weight / number of ester groups) of the active ester compound is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 150 g / eq to 400 g / eq, more preferably 170 g / eq to 300 g / eq, and even more preferably 200 g / eq to 250 g / eq. The ester equivalent of the active ester compound is a value measured by a method in accordance with JIS K 0070:1992.

[0041] The curing agent may contain other curing agents besides the active ester compound. Examples of other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. Among these, phenol curing agents are preferred. The molding resin composition may contain only one type of other curing agent, or two or more types.

[0042] -Phenol Curing Agent- Specific examples of the phenol curing agent include polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolak-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde, under an acidic catalyst; and resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or the like. Examples of the phenolic curing agent include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; paraxylylene-modified phenolic resins and metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above-mentioned phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerization of two or more of these. These phenolic curing agents may be used alone or in combination of two or more.

[0043] The hydroxyl equivalent of the phenolic curing agent is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, the hydroxyl equivalent of the phenolic curing agent is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq. The hydroxyl equivalent of the phenolic curing agent is a value measured by a method in accordance with JIS K 0070:1992.

[0044] The equivalent ratio between the epoxy resin and the curing agent, i.e., the ratio of the number of functional groups in the curing agent (preferably the number of ester groups or the total number of ester groups and hydroxyl groups) to the number of functional groups in the epoxy resin (preferably the number of epoxy groups) (number of functional groups in the curing agent / number of functional groups in the epoxy resin), is not particularly limited. From the viewpoint of minimizing unreacted amounts of each, it is preferably 0.5 to 2.0, more preferably 0.6 to 1.3. From the viewpoints of moldability and reflow resistance, it is even more preferably 0.8 to 1.2.

[0045] When an active ester compound and a phenolic curing agent are used in combination as the curing agent, the molar ratio of the ester groups contained in the active ester compound to the phenolic hydroxyl groups contained in the phenolic curing agent (ester groups / phenolic hydroxyl groups) is preferably 9 / 1 to 1 / 9, more preferably 8 / 2 to 2 / 8, and even more preferably 3 / 7 to 7 / 3.

[0046] When an active ester compound and another curing agent (preferably a phenolic curing agent) are used in combination as a curing agent, the mass proportion of the active ester compound in the total amount of the active ester compound and the other curing agent (preferably a phenolic curing agent) is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, and even more preferably 55% by mass to 70% by mass, from the viewpoint of achieving excellent flexural strength after curing of the molding resin composition and of keeping the dielectric dissipation factor of the cured product low.

[0047] The softening point or melting point of the active ester compound as the curing agent and other curing agents such as a phenolic curing agent used as needed are not particularly limited. From the viewpoints of moldability and reflow resistance, the softening point or melting point of the curing agent is preferably 40°C to 180°C, and from the viewpoint of handleability during production of the molding resin composition, it is more preferably 50°C to 130°C. The melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0048] (Inorganic Filler) The molding resin composition of the present disclosure contains an inorganic filler. The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, aluminum nitride, boron nitride, talc, clay, mica, and titanium compounds such as calcium titanate. An inorganic filler having a flame-retardant effect may also be used. Examples of inorganic fillers having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

[0049] Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. Boron nitride is preferred from the viewpoint of further reducing the dielectric loss tangent. One type of inorganic filler may be used alone, or two or more types may be used in combination. The inorganic filler may be in the form of powder, beads obtained by spheroidizing powder, fiber, etc.

[0050] The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 50 μm, and more preferably 0.5 μm to 30 μm. When the volume average particle diameter is 0.2 μm or more, an increase in viscosity of the molding resin composition tends to be further suppressed. When the volume average particle diameter is 50 μm or less, the ability to fill narrow gaps tends to be further improved. The volume average particle diameter of the inorganic filler refers to the value measured as the volume average particle diameter (D50) using a laser diffraction scattering particle size distribution measuring device.

[0051] The volume average particle size of the inorganic filler in the molding resin composition or its cured product can be measured by a known method. For example, the inorganic filler is extracted from the molding resin composition or its cured product using an organic solvent, nitric acid, aqua regia, or the like, and then thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion. Using this dispersion, the volume average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer. Alternatively, the cured product can be embedded in a transparent epoxy resin or the like, polished, and the resulting cross-section observed using a scanning electron microscope to obtain a volume-based particle size distribution. Furthermore, the volume average particle size of the inorganic filler can also be measured by continuously observing two-dimensional cross-sections of the cured product using an FIB device (focused ion beam SEM) or the like, followed by three-dimensional structural analysis.

[0052] From the viewpoint of the fluidity of the molding resin composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably wide.

[0053] From the viewpoint of a low dielectric constant and high fracture energy of the cured product, the total content of inorganic fillers contained in the molding resin composition is preferably more than 40% by volume, more preferably more than 50% by volume, even more preferably more than 50% by volume but not more than 80% by volume, and particularly preferably 55% to 70% by volume, based on the total volume of the molding resin composition.

[0054] The content (volume %) of inorganic filler in a molding resin composition can be determined by the following method. A thin section sample of the cured molding resin composition is imaged using a scanning electron microscope (SEM). An arbitrary area S is identified in the SEM image, and the total area A of the inorganic fillers contained in area S is determined. The total area A of the inorganic fillers is divided by area S to convert it to a percentage (%), and this value is used as the content (volume %) of inorganic filler in the molding resin composition. Area S is set to an area sufficiently large relative to the size of the inorganic filler. For example, it is set to a size that contains 100 or more inorganic fillers. Area S may be the sum of multiple cross sections. The inorganic filler may have a bias in its presence in the direction of gravity when the molding resin composition is cured. In this case, when imaging with an SEM, the entire cured product is imaged in the direction of gravity, and the area S containing the entire cured product in the direction of gravity is determined.

[0055] (Porous polymer particles) The molding resin composition of the present disclosure contains porous polymer particles. By replacing a portion of the inorganic filler with the porous polymer particles, it is possible to lower the relative dielectric constant while maintaining a low dielectric loss tangent.

[0056] The porous polymer particles are not particularly limited as long as they are porous particles containing a polymer. The porous polymer particles preferably contain at least one polymer selected from the group consisting of a (meth)acrylic polymer, an olefin polymer, a styrene polymer, and a urethane polymer. From the viewpoint of reducing the dimensional change before and after curing of a molded article made from the molding resin composition, the porous polymer particles preferably contain a styrene polymer.

[0057] The porous polymer particles may have a core having a porous shape and a shell covering at least a portion of the core. The porous core has some pores located on the surface, resulting in an uneven surface. By covering the core with the shell, at least a portion of the uneven surface is covered with the shell layer. Therefore, the surface of the porous polymer particles tends to be smoother. It is presumed that this results in increased fluidity of the molding resin composition.

[0058] The material of the core layer is not particularly limited, and examples thereof include (meth)acrylic polymers, olefin polymers, styrene polymers, and urethane polymers.

[0059] The material for the shell layer is not particularly limited, and examples thereof include (meth)acrylic resin and styrene resin.

[0060] The average particle size of the porous polymer particles may be 1 μm to 15 μm, 3 μm to 12 μm, or 5 μm to 10 μm. The average particle size of the porous polymer particles may be a value measured as a volume average particle size (D50) using a laser diffraction scattering particle size distribution measuring device, or may be the arithmetic mean value of particle sizes of 100 porous polymer particles randomly selected by observing the cross section of a composition, a cured product, or the like using an SEM (scanning electron microscope).

[0061] The porous polymer particles are preferably thermosetting. When the porous polymer has thermosetting properties, the porous polymer reacts with itself and expands when heated, thereby reducing the dimensional change before and after curing of a molded product made from the molding resin composition. As a result, warping of an electronic component device including a cured product of the molding resin composition tends to be reduced.

[0062] The porous polymer particles may be hollow particles. When the porous polymer particles are hollow particles, the hollowness of the porous polymer particles is preferably 30% to 70%, more preferably 40% to 60%, from the viewpoint of a balance between low dielectric constant, kneadability, and fluidity. For example, when the hollowness of the porous polymer particles is 30% or more, the dielectric constant of the cured product tends to be lower. When the hollowness of the porous polymer particles is 70% or less, the kneadability and fluidity of the molding resin composition tend to be excellent. The hollowness can be measured by the following method. When hollow particles are observed with a transmission electron microscope, solid and hollow portions with different contrasts are observed. The length of each portion toward the center of the hollow particle is measured, and the volume is calculated from this value to determine the hollowness.

[0063] From the viewpoint of a low dielectric constant and high fracture energy of the cured product, the content of the porous polymer particles is preferably 5 to 50% by volume, more preferably 8 to 40% by volume, and even more preferably 10 to 30% by volume, based on the total amount of the inorganic filler and the porous polymer particles.

[0064] From the viewpoint of a low dielectric loss tangent and high breaking energy of the cured product, the content of the porous polymer particles is preferably 3 to 40% by volume, more preferably 5 to 30% by volume, and even more preferably 8 to 20% by volume, relative to the total amount of the molding resin composition.

[0065] [Various Additives] In addition to the components described above, the molding resin composition of the present disclosure may or may not independently contain various additives such as a curing accelerator, a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, and a stress relaxation agent, as exemplified below. The molding resin composition of the present disclosure may also contain various additives known in the technical field as needed, in addition to the additives exemplified below.

[0066] (Curing Accelerator) The molding resin composition of the present disclosure may contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected depending on the type of epoxy resin, the desired properties of the molding resin composition, and the like. One type of curing accelerator may be used alone, or two or more types may be used in combination. Specific examples of curing accelerators are listed below, but are not limited thereto. Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and the addition of maleic anhydride to these compounds, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone. quinone compounds such as benzophenone, and compounds having intramolecular polarization obtained by adding a compound having a π bond, such as diazophenylmethane; cyclic amidinium compounds such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide;organic phosphines such as primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, and tris(benzyl)phosphine; phosphine compounds such as complexes of the organic phosphines with organic borons; and complexes of the organic phosphines or the phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, compounds having intramolecular polarization obtained by adding a compound having a π bond, such as quinone compounds, such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and anthraquinone, or diazophenylmethane; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound such as bromo-1-naphthol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation step;Examples of suitable curing accelerators include tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted phosphonium with phenolic compounds; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. Suitable curing accelerators include triphenylphosphine and adducts of triphenylphosphine with quinone compounds.

[0067] When the molding resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.1 to 8 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 6 parts by mass, per 100 parts by mass of the total amount of the epoxy resin and curing agent. By setting the content of the curing accelerator within the above range, the curing rate of the molding resin composition of the present disclosure becomes an appropriate value, making it easy to produce molded articles.

[0068] (Coupling Agent) The molding resin composition of the present disclosure may contain a coupling agent. From the viewpoint of improving the adhesion between the epoxy resin and the curing agent and the inorganic filler, the molding resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate-based compounds, and aluminum / zirconium-based compounds.

[0069] When the molding resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass, per 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, the adhesiveness tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

[0070] (Ion Exchanger) The molding resin composition of the present disclosure may contain an ion exchanger. The molding resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an encapsulated electronic component. The ion exchanger is not particularly limited, and conventionally known ion exchangers can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchangers may be used alone or in combination of two or more. Among these, hydrotalcites represented by the following general formula (A) are preferred:

[0071] Mg （１－Ｘ） Al Ｘ (OH) ２ (CO ３ ) Ｘ／２ ・mH ２ O ……(A) (0<X≦0.5, m is a positive number)

[0072] When the molding resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, the content of the ion exchanger is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin and curing agent combined.

[0073] (Mold Release Agent) The molding resin composition of the present disclosure may contain a mold release agent from the viewpoint of obtaining good mold releasability during molding. There are no particular limitations on the mold release agent, and conventionally known mold release agents can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. One type of mold release agent may be used alone, or two or more types may be used in combination.

[0074] When the molding resin composition contains a release agent, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin component. When the amount of the release agent is 0.01 part by mass or more per 100 parts by mass of the resin component, sufficient releasability tends to be obtained. When the amount of the release agent is 10 parts by mass or less per 100 parts by mass of the resin component, better adhesion tends to be obtained.

[0075] (Flame Retardant) The molding resin composition of the present disclosure may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0076] When the molding resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect. For example, the amount of the flame retardant is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the epoxy resin and curing agent combined.

[0077] (Colorant) The molding resin composition of the present disclosure may contain a colorant. Examples of colorants include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. One type of colorant may be used alone, or two or more types may be used in combination.

[0078] (Stress Relaxant) The molding resin composition of the present disclosure may contain a stress relaxation agent. By including a stress relaxation agent, warpage of the package and the occurrence of package cracks can be further reduced. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexibilizers). Specific examples include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers; indene-styrene-coumarone copolymers; organic phosphorus compounds such as triphenylphosphine oxide and phosphate esters; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. One type of stress relaxation agent may be used alone, or two or more types may be used in combination. Examples of silicone-based stress relaxation agents include those having an epoxy group, those having an amino group, and those modified with polyether, and silicone compounds such as silicone compounds having an epoxy group and polyether-based silicone compounds are more preferred.

[0079] From the viewpoint of the dielectric loss tangent, the stress relaxation agent preferably contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide.

[0080] When the molding resin composition contains a stress relaxation agent, the amount thereof is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the epoxy resin and the curing agent combined. When the stress relaxation agent contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide, the amount thereof is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the epoxy resin and the curing agent combined. The content of the silicone-based stress relaxation agent may be, for example, 2 parts by mass or less, or 1 part by mass or less, per 100 parts by mass of the epoxy resin and the curing agent combined. The molding resin composition may not contain a silicone-based stress relaxation agent. The lower limit of the content of the silicone-based stress relaxation agent is not particularly limited, and may be 0 parts by mass or 0.1 parts by mass.

[0081] From the viewpoint of dielectric loss tangent, the content of the silicone-based stress relaxation agent is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less, and extremely preferably 0.5% by mass or less, relative to the entire molding resin composition. The lower limit of the content of the silicone-based stress relaxation agent is not particularly limited, and may be 0% by mass or 0.1% by mass.

[0082] (Method for preparing molding resin composition) The method for preparing the molding resin composition is not particularly limited. A common method includes thoroughly mixing predetermined amounts of components using a mixer or the like, melt-kneading the mixture using a mixing roll, extruder, or the like, cooling, and pulverizing the mixture. More specifically, a method includes stirring and mixing predetermined amounts of the components described above, kneading the mixture using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, cooling, and pulverizing the mixture.

[0083] The molding resin composition of the present disclosure is preferably solid at room temperature and normal pressure (e.g., 25°C, atmospheric pressure). When the molding resin composition is solid, its shape is not particularly limited, and examples include powder, granules, tablets, etc. When the molding resin composition is in tablet form, it is preferable that the dimensions and mass of the tablet-shaped molding resin composition be such that they are suitable for the molding conditions of the package, from the viewpoint of ease of handling.

[0084] (Uses of Molding Resin Composition) The molding resin composition of the present disclosure can be applied, for example, to the production of electronic component devices, particularly high-frequency devices, as described below. The molding resin composition of the present disclosure may be used to seal electronic components in high-frequency devices. In particular, with the recent spread of fifth-generation mobile communication systems (5G), semiconductor packages (PKGs) used in electronic component devices have become increasingly sophisticated and compact. As PKGs become smaller and more sophisticated, the development of antenna-in-package (AiP), which is a PKG with antenna functionality, is also progressing. In AiP, radio waves used for communication are becoming higher in frequency to accommodate the increase in the number of channels associated with the diversification of information, and sealing materials are required to have a low dielectric loss tangent. As described above, the molding resin composition of the present disclosure can produce a cured product with a low dielectric loss tangent. Therefore, the molding resin composition is particularly suitable for antenna-in-package (AiP) applications in high-frequency devices, in which an antenna arranged on a support member is sealed with the molding resin composition. In an electronic component device including an antenna such as an antenna-in-package, heat is generated by power supply when a power supply amplifier is provided on the opposite side of the antenna. From the viewpoint of improving heat dissipation, it is preferable that the molding resin composition used in manufacturing the electronic component device contains alumina particles as an inorganic filler.

[0085] The electronic component device of the present disclosure includes a support member, an electronic component disposed on the support member, and a cured product of the molding resin composition encapsulating the electronic component. Examples of the electronic component device include a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, on which electronic components (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, and antennas) are mounted, and the resulting electronic component region is encapsulated with the molding resin composition (e.g., a high-frequency device).

[0086] The type of the support member is not particularly limited, and a support member generally used in the manufacture of electronic component devices can be used. The electronic component may include an antenna, or may include an antenna and an element other than an antenna. The antenna is not limited as long as it functions as an antenna, and may be an antenna element or wiring.

[0087] In the electronic component device of the present disclosure, if necessary, another electronic component may be disposed on the surface of the support member opposite to the surface on which the electronic component is disposed. The other electronic component may be encapsulated with the molding resin composition described above, with another resin composition, or may not be encapsulated.

[0088] (Method for manufacturing an electronic component device) The method for manufacturing an electronic component device of the present disclosure includes a step of placing an electronic component on a support member and a step of encapsulating the electronic component with the molding resin composition. The method for carrying out each of the above steps is not particularly limited, and can be carried out by a general method. Furthermore, the types of support member and electronic component used in manufacturing the electronic component device are not particularly limited, and support members and electronic components commonly used in manufacturing electronic component devices can be used.

[0089] Methods for encapsulating electronic components using the molding resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is the most common.

[0090] The above-described embodiment will be specifically described below using examples, but the scope of the above-described embodiment is not limited to these examples.

[0091] <Preparation of molding resin compositions> The components shown below were mixed in the blending ratios (parts by mass) shown in Table 1 to prepare molding resin compositions for Examples and Comparative Examples. This molding resin composition was solid at room temperature and normal pressure. In Table 1, "-" means that the component was not included. In Table 1, the filler refers to the total of the inorganic filler and porous polymer.

[0092] Epoxy resin 1: biphenyl type epoxy resin, epoxy equivalent 192 g / eq Epoxy resin 2: triphenylmethane type epoxy resin, epoxy equivalent 169 g / eq Epoxy resin 3: o-cresol novolac type epoxy resin, epoxy equivalent 200 g / eq Curing agent: activated ester compound, DIC Corporation, product name "EXB-8", ester equivalent 213 g / eq Curing accelerator: adduct of tributylphosphine and 1,4-benzoquinone Coupling agent 1: 3-glycidoxypropyltrimethoxysilane Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane Colorant: carbon black Filler 1: silica powder, which is an inorganic filler, volume average particle size 0.5 μm, specific gravity 2.2 g / cm ３ Filler 2: Silica powder, an inorganic filler, volume average particle size 4.0 μm, specific gravity 2.2 g / cm ３ Filler 3: Porous polymer particles, polymethyl methacrylate particles, volume average particle size 8 μm, maximum particle size 20 μm, spherical, thermal decomposition temperature 265° C., hollowness 45%, specific gravity 0.6 g / cm ３ Filler 4: acrylic urethane polymer particles, which are porous polymer particles, with a volume average particle size of 6 μm, spherical shape, thermal decomposition temperature of 280° C., and specific gravity of 0.6 g / cm ３ Filler 5: Porous polymer particles, styrene polymer particles having a shell layer (material: styrene resin), low oil absorption, volume average particle size 7 μm, maximum particle size 20 μm, spherical, thermal decomposition temperature 280° C., hollowness 45%, specific gravity 0.6 g / cm ３Filler 6: Porous polymer particles, styrene polymer particles having a shell layer (material: styrene resin), low oil absorption, volume average particle size 7.5 μm, maximum particle size 20 μm, spherical, thermal decomposition temperature 290° C., hollowness 50%, specific gravity 0.6 g / cm ３

[0093] The volume-average particle size of each inorganic filler was a value obtained by the following measurement. Specifically, the inorganic filler was first added to a dispersion medium (water) in an amount ranging from 0.01% by mass to 0.1% by mass, and the mixture was dispersed in a bath-type ultrasonic cleaner for 5 minutes. Five ml of the resulting dispersion was poured into a cell, and the particle size distribution was measured at 25°C using a laser diffraction scattering particle size distribution analyzer (HORIBA, Ltd., LA920). The particle size at an integrated value of 50% (volume basis) in the resulting particle size distribution was taken as the volume-average particle size.

[0094] (Evaluation of spiral flow (SF)) Using a spiral flow measurement mold conforming to EMMI-1-66, the molding resin composition was molded with a transfer molding machine under conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds, and the flow distance (cm) was determined. The results are shown in Table 1.

[0095] (Room temperature bending test) The molding resin composition was charged into a transfer molding machine and molded under conditions of a mold temperature of 175 ° C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds. Post-curing was performed at 175 ° C for 6 hours to prepare a rectangular parallelepiped test piece measuring 127 mm x 12.7 mm x 4 mm. Using a Tensilon (A & D Co.) as an evaluation device, a three-point support bending test in accordance with JIS-K-7171 (2016) was performed at room temperature (25 ° C), and the flexural modulus E, flexural strength S, and elongation at break ε of the test piece were calculated using the following formula.

[0096] The flexural modulus E (GPa), flexural strength S (MPa), and breaking elongation ε (%) are defined by the following formula. In the formula, P is the load cell 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. For the flexural modulus E, the value calculated using the formula described below was converted to GPa.

[0097]

[0098]

[0099]

[0100] (Measurement of Breaking Energy) The molding resin composition was subjected to the bending test described above, and the area of ​​the S-S curve of breaking elongation (%) and bending strength (MPa) was calculated using the following formula, and this value was taken as the breaking energy. Figure 1 shows the S-S curves of breaking elongation and bending strength calculated using the molding resin compositions of each Example and Comparative Example. The results are shown in Table 1.

[0101]

[0102] (Molding Shrinkage Measurement) The molding resin composition was molded using a transfer molding machine under conditions of a molding temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (length 127 mm, width 12.7 mm, thickness 6.4 mm). The mold shrinkage A (%) (mold shrinkage AM in Table 1) was calculated using the following formula from the mold cavity length D at 25°C, which had been measured in advance, and the molded product length d at room temperature (25°C). The results are shown in Table 1. Mold shrinkage A (%) = ((D - d) / D) x 100

[0103] The molding resin composition was molded using a transfer molding machine under conditions of a molding temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (127 mm long, 12.7 mm wide, 6.4 mm thick). The molded product was post-cured for 5 hours at 175°C to obtain a plate-shaped cured product. The mold shrinkage B (%) (molding shrinkage AC in Table 1) was calculated using the following formula from the mold cavity length D at 25°C, which was measured in advance, and the length d of the cured product at room temperature (25°C). The results are shown in Table 1. Mold shrinkage B (%) = ((D - d) / D) x 100

[0104] (Measurement of relative permittivity and dielectric loss tangent) The encapsulating resin composition was charged into a transfer molding machine and molded under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Post-curing was performed at 175°C for 6 hours to obtain a rod-shaped cured product (length 90 mm, width 0.6 mm, thickness 0.8 mm). This cured product was used as a test specimen to measure the relative permittivity (Dk) and dielectric loss tangent (Df) at a temperature of 25±3°C and 10 GHz using a cavity resonator (Kanto Electronics Application Development Co., Ltd.) and a network analyzer (Keysight Technologies, product name "PNA E8364B"). The cavity resonator used was of the following model: 10 GHz...CP531

[0105]

[0106] As is clear from the evaluation results in Table 1, the cured products of the molding resin compositions of Examples 1 and 2 had a lower dielectric constant than the cured product of the molding resin composition of Comparative Example 1, which used the same type of epoxy resin. The cured products of the molding resin compositions of Examples 3 to 6 had a lower dielectric constant than the cured product of the molding resin composition of Comparative Example 2, which used the same type of epoxy resin. Furthermore, in Examples 4 to 6, it was confirmed that the mold shrinkage after curing tended to decrease as the amount of filler 5, which was porous polymer particles, increased.

[0107] (Confirmation of change in viscoelastic properties due to heating) The filler 5 was subjected to viscoelasticity measurement in an unheated state (0 h) and after heating at 175°C for 5 minutes, 2 hours, or 6 hours. For the viscoelasticity measurement, test samples were prepared in an unheated state (0 h) and after heating at 175°C for 5 minutes, 2 hours, or 6 hours, and measured using a rotational rheometer Kinexus lab+ (manufactured by NETZSCH Japan Co., Ltd.) under the conditions of amplitude method, strain = 0.1%, frequency = 1 Hz, gap = 0.5 mm, measurement temperature range 25°C to 180°C, and temperature rise rate 10°C / min. The results are shown in Figure 2. 1.00E + 0X (X is an integer) in Figure 2 means 10 Ｘ (10 to the power of X).

[0108] As shown in Figure 2, the sample obtained by heating the composition had a high elastic modulus at the measurement temperature. From this result, it is inferred that Filler 5 has self-reactivity upon heating (i.e., thermosetting properties).

[0109] The disclosure of Japanese Patent Application No. 2022-188706, filed on November 25, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A molding resin composition comprising an epoxy resin, a curing agent containing an active ester compound, an inorganic filler, and porous polymer particles.

2. The molding resin composition according to claim 1, wherein the porous polymer particles include a core portion having a porous shape and a shell portion covering at least a part of the core portion.

3. The molding resin composition according to claim 1, wherein the porous polymer particles include a core portion having a porous shape, and the core portion includes at least one polymer selected from the group consisting of (meth)acrylic polymers, olefin polymers, styrene polymers, and urethane polymers.

4. The molding resin composition according to claim 1, wherein the content of the porous polymer particles is 5% to 50% by volume based on the total amount of the inorganic filler and the porous polymer particles.

5. The molding resin composition according to claim 1, wherein the content of the porous polymer particles is 3% to 40% by volume based on the total amount of the molding resin composition.

6. The molding resin composition according to claim 1, wherein the porous polymer particles have thermosetting properties.

7. The molding resin composition according to any one of claims 1 to 6, which is used for a high-frequency device.

8. The molding resin composition according to claim 7, which is used for encapsulating electronic components in a high-frequency device.

9. The molding resin composition according to claim 7, which is used for an antenna-in-package.

10. A support member, electronic components disposed on the support member, and a cured product of the molding resin composition according to any one of claims 1 to 6, which encapsulates the electronic components. An electronic component device comprising the above.

11. The electronic component device according to claim 10, wherein the electronic component includes an antenna.