Resin composition, electronic component device, and method for producing resin composition

Abstract

A resin composition containing a curable resin and carbon particles, the carbon particles satisfy at least one of (1) and (2) below. (1) The pH is 5.0 or less, and (2) the average particle size is 80 nm or more.

Description

Resin composition, electronic component device, and method for producing resin composition

[0001] The present disclosure relates to a resin composition, an electronic component device, and a method for producing the resin composition.

[0002] In recent wireless communication fields, radio waves have become increasingly frequent due to an increase in the number of channels and the amount of information transmitted. The amount of transmission loss of electrical signals used in wireless communication (dielectric loss) caused by insulators, such as circuit encapsulants, increases in proportion to the product of the frequency of the radio waves, the square root of the insulator's dielectric constant, and the insulator's dielectric loss tangent. Therefore, as the frequency of radio waves increases, reducing the insulator's dielectric constant or dielectric loss tangent is becoming increasingly important from the perspective of suppressing transmission loss of electrical signals.

[0003] For example, Patent Documents 1 and 2 disclose a resin composition containing an active ester resin as a curing agent for an epoxy resin, and it is said that an insulator obtained by curing this resin composition has a low dielectric loss tangent.

[0004] Patent Document 1: JP 2012-246367 A Patent Document 2: JP 2014-114352 A

[0005] The cured products of the resin compositions described in Patent Documents 1 and 2 have low dielectric dissipation factors and can contribute to reducing dielectric loss, but there is a limit to the amount of curing agent that can be contained in the resin composition. Therefore, there is a need for the development of a technology for reducing the dielectric dissipation factor of the cured product by means other than a curing agent. The present disclosure has been made in consideration of the above circumstances, and aims to provide a resin composition that can yield a cured product with a low dielectric dissipation factor, an electronic component device obtained using this resin composition, and a method for producing this resin composition.

[0006] Specific means for solving the above problems include the following aspects. <1> A resin composition comprising a curable resin and carbon particles, wherein the carbon particles satisfy at least one of the following (1) and (2): (1) A pH of 5.0 or less; (2) An average particle diameter of 80 nm or more. <2> The resin composition according to <1>, wherein the carbon particles satisfy at least (1). <3> The resin composition according to <1>, wherein the carbon particles satisfy at least (2). <4> The resin composition according to any one of <1> to <3>, wherein the carbon particles contain carbon black. <5> The resin composition according to any one of <1> to <4>, wherein the curable resin contains an epoxy resin. <6> An electronic component device comprising: a support member; an electronic component placed on the support member; and a cured product of the resin composition according to any one of <1> to <5> that encapsulates the electronic component. <7> The electronic component device according to <6>, wherein the electronic component includes an antenna. <8> A method for producing a resin composition, comprising mixing a curable resin with carbon particles, the carbon particles satisfying at least one of the following (1) and (2): (1) a pH of 5.0 or less, and (2) an average particle size of 80 nm or more.

[0007] According to the present disclosure, there are provided a resin composition that gives a cured product with a low dielectric loss tangent, an electronic component device obtained using this resin composition, and a method for producing this resin composition.

[0008] 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 staged numerical range. 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, each component may contain multiple types of particles. When multiple types of particles corresponding to each component are present in the 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.

[0009] Hereinafter, embodiments for carrying out 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.

[0010] <Resin Composition> A resin composition according to one embodiment of the present disclosure includes a curable resin and carbon particles, and the carbon particles satisfy at least one of the following (1) and (2): (1) a pH of 5.0 or less; and (2) an average particle diameter of 80 nm or more.

[0011] Resin compositions used to seal electronic components may contain carbon particles such as carbon black for purposes such as coloring, light blocking, and assisting in laser marking. Carbon particles are generally conductive and are therefore thought to contribute to increasing the dielectric loss tangent of the cured product. In this embodiment, the carbon particles contained in the resin composition satisfy at least one of (1) and (2). This is thought to contribute to reducing the dielectric loss tangent of the cured product of the resin composition.

[0012] Each component constituting the resin composition will be described below. The resin composition of the present embodiment contains a curable resin and carbon particles, and may contain other components as needed.

[0013] (Carbon Particles) The resin composition of the present embodiment contains carbon particles. In the present disclosure, carbon particles refer to particulate substances in which 90% by mass or more of all elements are carbon.

[0014] Examples of carbon particles include amorphous carbon particles such as carbon black, carbon fiber, and activated carbon, and crystalline carbon particles such as fullerene, carbon nanotube, graphene, and graphite. Among these, amorphous carbon particles are preferred, and carbon black is more preferred. The type of carbon black is not particularly limited and can be selected depending on the desired properties. The carbon black can be selected from, for example, furnace black, channel black, acetylene black, and thermal black. The resin composition may contain only one type of carbon particle or two or more types of carbon particles.

[0015] From the viewpoint of reducing the dielectric loss tangent of the cured resin composition, the pH of the carbon particles is preferably 5.0 or less. Carbon particles with a pH of 5.0 or less are thought to contain a relatively large amount of polar groups, such as carboxy groups, and to be in a state in which the movement of electrons between carbon particles is easily inhibited by the polar groups (which may be in a state of reaction with components in the resin composition). As a result, the dielectric loss tangent of the cured resin composition containing the carbon particles is thought to be reduced.

[0016] The pH of the carbon particles is more preferably 4.5 or less, and even more preferably 4.0 or less. From the viewpoint of preventing corrosion of metal members such as wires, the pH of the carbon particles is preferably 3.0 or more.

[0017] In the present disclosure, the pH of the carbon particles is a value measured at 25°C by the boiling extraction method specified in JIS K5101-17-1 (2004).

[0018] From the viewpoint of reducing the dielectric loss tangent of the cured resin composition, the average particle size of the carbon particles is preferably 80 nm or more. Carbon particles with an average particle size of 80 nm or more are thought to have a relatively small specific surface area, making it difficult for electrons to move between the carbon particles. As a result, it is thought that the dielectric loss tangent of the cured resin composition containing the carbon particles is reduced.

[0019] The average particle size of the carbon particles is preferably 90 nm or more, and more preferably 100 nm or more. From the viewpoint of dispersibility of the carbon particles, the average primary particle size of the carbon particles is preferably 1000 nm or less, and more preferably 500 nm or less.

[0020] In the present disclosure, the average particle size of carbon particles is measured by image analysis. The image analysis method is not particularly limited. For example, carbon particles may be observed using an optical microscope or an electron microscope. Carbon particles may be counted visually or using an image analysis system. From the viewpoint of measurement accuracy, image analysis is performed under conditions where the total number of carbon particles to be measured is 100 or more and the observation magnification is 1000 times or more. The arithmetic mean value of the particle sizes of the carbon particles to be measured is taken as the average particle size of the carbon particles. The particle size of the carbon particles to be measured is taken as the circle-equivalent diameter of the observed particles. When the carbon particles form aggregates, the particle size of the carbon particles is taken as the particle size of the particles (primary particles) forming the aggregates.

[0021] The content of carbon particles contained in the resin composition is not particularly limited. From the viewpoint of achieving a desired purpose such as coloring, the content of carbon particles is preferably 0.1 mass% or more of the entire resin composition, and more preferably 0.3 mass% or more. From the viewpoint of keeping the dielectric loss tangent of the cured product low, the content of carbon particles is preferably 5 mass% or less of the entire resin composition, and more preferably 1 mass% or less.

[0022] (Curable Resin) The resin composition in this embodiment contains a curable resin. The curable resin may be either a thermosetting resin or a photocurable resin, and from the viewpoint of mass production, a thermosetting resin is preferred. Examples of thermosetting resins include epoxy resins, phenolic resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, polyimide resins such as bismaleimide resins, polyamide resins, polyamideimide resins, silicone resins, and acrylic resins. From the viewpoint of moldability and electrical properties, the thermosetting resin is preferably at least one selected from the group consisting of epoxy resins and polyimide resins, more preferably at least one selected from the group consisting of epoxy resins and bismaleimide resins, and even more preferably an epoxy resin. The resin composition may contain only one type of curable resin, or may contain two or more types. Hereinafter, an epoxy resin will be described as an example of a curable resin.

[0023] -Epoxy Resin- The resin composition preferably contains an epoxy resin as the curable resin. When the resin composition contains an epoxy resin as the curable resin, the content of the epoxy resin relative to the total curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.

[0024] Specific examples of epoxy resins include novolac epoxy resins (phenol novolac epoxy resins, orthocresol novolac epoxy resins, etc.) obtained by epoxidizing novolac resins 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, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc.; triphenylmethane epoxy resins obtained by epoxidizing triphenylmethane phenolic resins obtained by condensing or co-condensing, under an acidic catalyst, the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc.; and novolac resins obtained by co-condensing, under an acidic catalyst, the above-mentioned phenolic compound and naphthol compound with 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; sulfur-containing epoxy resins which are diglycidyl ethers of bisphenol S, or the like; 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 in which a co-condensation resin of dicyclopentadiene and a phenolic compound is epoxidized.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 produced 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 dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include pentadiene-modified epoxy resins, cyclopentadiene-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. These epoxy resins may be used alone or in combination of two or more.

[0025] 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.

[0026] 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 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).

[0027] When the resin composition contains an epoxy resin as a curable resin, the mass proportion of the epoxy resin in the total amount of the resin composition is preferably 0.5 mass % to 30 mass %, more preferably 2 mass % to 20 mass %, and even more preferably 3.5 mass % to 13 mass %, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like.

[0028] - Curing Agent - When the resin composition contains an epoxy resin as the curable resin, the resin composition may further contain a curing agent.

[0029] From the viewpoint of reducing the dielectric loss tangent of the cured product, it is preferable that the resin composition contains an active ester compound as a curing agent. The active ester compounds may be used alone or in combination of two or more. Here, the active ester compound refers to a compound that has one or more ester groups per molecule that react with epoxy groups and has the ability to harden epoxy resins. Note that when the curing agent contains an active ester compound, the curing agent may or may not contain a curing agent other than the active ester compound.

[0030] When an active ester compound is used as a curing agent, the dielectric loss tangent of the cured product can be kept lower than when other curing agents (e.g., phenolic curing agents) are used. The reason for this is presumed to be as follows: In the reaction between an epoxy resin and a phenolic curing agent, secondary hydroxyl groups are generated. In contrast, in the reaction between an epoxy resin and an active ester compound, ester groups are generated instead of secondary hydroxyl groups. Since ester groups have lower polarity than secondary hydroxyl groups, a resin composition containing an active ester compound as a curing agent can keep the dielectric loss tangent of the cured product lower than a resin composition 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 By reducing the O content, the dielectric loss tangent of the cured product can be further reduced.

[0031] The type of active ester compound is not particularly limited as long as it has one or more ester groups in the molecule that react with an epoxy group. Examples of the active ester compound include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds.

[0032] 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.

[0033] 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.

[0034] 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.

[0035]

[0036] In structural formula (1), R １ represents 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 0.25 to 1.5.

[0037] 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.

[0038]

[0039]

[0040] 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.

[0041]

[0042] 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).

[0043] In structural formula (3), 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).

[0044] Specific examples of the compound represented by structural formula (2) include the following exemplary compounds (2-1) to (2-6).

[0045]

[0046] Specific examples of the compound represented by structural formula (3) include the following exemplary compounds (3-1) to (3-6).

[0047]

[0048] 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.

[0049] 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.

[0050] The curing agent may contain other curing agents in addition to the active ester compound. The type of other curing agent is not particularly limited and can be selected depending on the desired properties of the resin composition. 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.

[0051] Specific examples of the phenolic curing agent include polyhydric phenolic 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, and 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.

[0052] The functional group equivalent of the other curing agent (hydroxyl group equivalent in the case of a phenolic curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of the other curing agent is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq. The functional group equivalent of the other curing agent (hydroxyl group equivalent in the case of a phenolic curing agent) is a value measured by a method in accordance with JIS K 0070:1992.

[0053] The softening point or melting point of the curing agent is not particularly limited. From the viewpoint 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 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.

[0054] The equivalent ratio between the epoxy resin and the curing agent (all curing agents when multiple curing agents are used), i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (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 components, it is preferably set in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is even more preferably set in the range of 0.8 to 1.2.

[0055] When the curing agent contains an active ester compound and other curing agents, the mass proportion of the active ester compound in the total amount of the active ester compound and other curing agents is preferably 40 mass % or more, more preferably 50 mass % or more, and even more preferably 60 mass % or more, from the viewpoint of keeping the dielectric loss tangent of the cured product low.

[0056] (Curing Accelerator) The resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected depending on the type of curable resin, the desired properties of the resin composition, and the like.

[0057] Examples of the curing accelerator used in the resin composition containing at least one selected from the group consisting of epoxy resins and polyimide resins as the curable resin include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and the like. cyclic amidine compounds such as 2-heptadecylimidazole and 2-heptadecylimidazole; derivatives of the above cyclic amidine compounds; phenol novolak salts of the above 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 quinone compounds such as phenyl-1,4-benzoquinone and phenyl-1,4-benzoquinone, 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(alkyl alkoxyphenyl)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 the organic phosphines or the phosphine compounds, which may be combined with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone. 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, and compounds having intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound such as 1-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-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl with the halogenated phenol compound, followed by a dehydrohalogenation step;Examples of the curing accelerator 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; salts of tetraalkylphosphonium with partial hydrolysates of aromatic carboxylic acid anhydrides; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0058] Among these, the curing accelerator is preferably a curing accelerator containing an organic phosphine. Examples of the curing accelerator containing an organic phosphine include the above-mentioned organic phosphines, phosphine compounds such as complexes of the above-mentioned organic phosphines and organoborons, and compounds having intramolecular polarization formed by adding a compound having a π bond to the above-mentioned organic phosphines or the above-mentioned phosphine compounds. Among these, particularly suitable curing accelerators include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, an adduct of tributylphosphine and a quinone compound, and an adduct of tri-p-tolylphosphine and a quinone compound.

[0059] When the resin composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin components (the total amount of the curable resin and the curing agent contained as needed; the same applies hereinafter). When the amount of the curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the resin components, the composition tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin components, the curing speed is not too fast and a good molded product tends to be obtained.

[0060] (Inorganic Filler) The resin composition may contain an inorganic filler. Specific examples of inorganic fillers include inorganic materials such as crystalline silica, fused silica, alumina, calcium titanate, barium titanate, glass, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. The resin composition may also contain an inorganic filler having a flame retardant effect. 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. One type of inorganic filler may be used alone, or two or more types may be used in combination.

[0061] From the viewpoint of increasing the thermal conductivity of the cured product, the resin composition preferably contains alumina particles as an inorganic filler. From the viewpoint of increasing the dielectric constant of the cured product, the resin composition preferably contains at least one inorganic filler selected from the group consisting of calcium titanate particles and barium titanate particles. From the viewpoint of increasing the dielectric constant of the cured product while reducing the dielectric loss tangent, the resin composition preferably contains calcium titanate particles as an inorganic filler. An inorganic filler that increases the dielectric constant of the cured product is suitable, for example, when the resin composition is used in the manufacture of an antenna-in-package type electronic component device described below.

[0062] When the resin composition contains alumina particles, the content of the alumina particles is preferably 30% by mass to 90% by mass, more preferably 40% by mass to 80% by mass, and even more preferably 50% by mass to 70% by mass, based on the total amount of the inorganic filler.

[0063] When the resin composition contains at least one selected from the group consisting of calcium titanate particles and barium titanate particles, the total content of the calcium titanate particles and barium titanate particles is preferably 10% by mass to 60% by mass, more preferably 20% by mass to 50% by mass, and even more preferably 30% by mass to 40% by mass, based on the total inorganic filler.

[0064] The volume average particle size of the inorganic filler is preferably 0.1 μm to 100 μm, more preferably 0.2 μm to 80 μm, and even more preferably 0.5 μm to 30 μm. The resin composition may contain two or more inorganic fillers having different volume average particle sizes.

[0065] The volume average particle size of the inorganic filler is the particle size at 50% cumulative (volume basis) in the particle size distribution obtained by laser diffraction / scattering. The particle size distribution is measured, for example, as follows. First, the inorganic filler is added to a dispersion medium (water) in an amount ranging from 0.01% to 0.1% by mass, and the mixture is dispersed in a bath-type ultrasonic cleaner for 5 minutes. Next, 5 ml of the resulting dispersion is poured into a cell, and the particle size distribution is measured at 25°C using a laser diffraction / scattering particle size distribution analyzer (HORIBA, Ltd., LA920).

[0066] The content of the inorganic filler is preferably 40% by volume to 90% by volume, more preferably 50% by volume to 85% by volume, and even more preferably 60% by volume to 80% by volume, based on the total volume of the resin composition.

[0067] When the composition of the resin composition is known, the content (volume %) of the inorganic filler in the resin composition can be calculated from the mass and density of each material contained in the resin composition. When the composition of the resin composition is unknown, the content (volume %) of the inorganic filler can be determined by the following method. A thin slice sample of the cured 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 the inorganic filler in the 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 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.

[0068] [Various Additives] In addition to the components described above, the resin composition may contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, stress relaxation agents, and fluidity imparting agents, as exemplified below. The resin composition may contain various additives known in the art, as needed, in addition to the additives exemplified below.

[0069] (Coupling Agent) The resin composition may contain a coupling agent. There are no particular limitations on the coupling agent, and conventionally known coupling agents can be used. Specific examples include silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, ureidosilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate-based compounds, and aluminum / zirconium-based compounds.

[0070] When the 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.

[0071] (Ion exchanger) The resin composition may contain an ion exchanger. There are no particular limitations on the ion exchanger, 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 exchanger may be used alone or in combination of two or more. Among these, hydrotalcites represented by the following general formula (A) are preferred.

[0072] Mg （１－Ｘ） Al Ｘ (OH) ２ (CO ３ ) Ｘ／２ ・mH ２ O ……(A) (0<X≦0.5, m is a positive number)

[0073] When the resin composition contains an ion exchanger, 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 resin component.

[0074] (Release Agent) The resin composition may contain a release agent. There are no particular limitations on the release agent, and conventionally known ones 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 release agent may be used alone, or two or more types may be used in combination.

[0075] When the 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.

[0076] (Flame retardant) The resin composition may contain a flame retardant. There are no particular limitations on the flame retardant, 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.

[0077] When the resin composition contains a flame retardant, 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 resin component.

[0078] (Stress Relaxant) The resin composition may contain a stress relaxation agent. By including a stress relaxation agent in the resin composition, warpage deformation of the package and the occurrence of package cracks can be further reduced. Examples of stress relaxation agents 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; 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. Among stress relaxation agents, silicone-based stress relaxation agents are preferred. 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] When the resin composition contains a stress relaxation agent, the amount of the stress relaxation agent is, for example, preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component.

[0080] (Fluidity Imparting Agent) The resin composition may contain a fluidity imparting agent. Specific examples of the fluidity imparting agent include indene coumarone resin and triphenylphosphine oxide.

[0081] When the resin composition contains a fluidity imparting agent, the amount of the fluidity imparting agent is, for example, preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component.

[0082] The resin composition is preferably solid at room temperature and normal pressure (for example, 25°C, atmospheric pressure). When the resin composition is solid, its shape is not particularly limited, and examples include powder, granules, tablets, etc. When the resin composition is in tablet form, it is preferable that the dimensions and mass of the tablet-shaped resin composition are such that they are suitable for the molding conditions of the package, from the viewpoint of handleability.

[0083] (Physical Properties of Resin Composition) The dielectric loss tangent at 10 GHz of the cured product obtained by compression molding the resin composition under conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 600 seconds is, for example, 0.020 or less. From the viewpoint of reducing transmission loss, the dielectric loss tangent at 10 GHz of the cured product is preferably 0.018 or less, more preferably 0.015 or less, and even more preferably 0.010 or less. The lower limit of the dielectric loss tangent at 10 GHz of the cured product is not particularly limited, and is, for example, 0.004. The dielectric loss tangent is measured by the method described in the examples.

[0084] When a resin composition is molded using a spiral flow measurement mold conforming to EMMI-1-66 under conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, the flow distance is preferably 60 cm or more, more preferably 70 cm or more, and even more preferably 80 cm or more. Hereinafter, the above flow distance will also be referred to as "spiral flow." The upper limit of the spiral flow is not particularly limited, and can be, for example, 200 cm. The spiral flow is measured by the method described in the examples.

[0085] The gel time of the resin composition at 175°C is preferably 30 to 100 seconds, and more preferably 40 to 70 seconds. The gel time of the resin composition at 175°C is measured as follows. Specifically, a 3 g sample of the resin composition is measured at 175°C using a Curelastometer manufactured by JSR Trading Co., Ltd., and the time until the torque curve rises is taken as the gel time (sec). The gel time is measured by the method described in the Examples.

[0086] (Uses of Resin Composition) The resin composition of the present embodiment provides a cured product with a reduced dielectric loss tangent, making the resin composition suitable for use as a sealant for electronic component devices that use high-frequency radio waves for communication.

[0087] As an electronic component device that uses high-frequency radio waves for communication, development is also underway for antenna-in-package (AiP), a package with antenna functionality. In AiP, the radio waves used for communication are becoming higher in frequency to accommodate the increase in the number of channels that accompanies the diversification of information, and therefore, encapsulants are required to have both a high relative dielectric constant and a low dielectric loss tangent.

[0088] Materials that increase the dielectric constant of the cured product of a resin composition (i.e., materials with a high dielectric constant) generally tend to also increase the dielectric dissipation factor of the cured product. The resin composition of this embodiment can reduce the dielectric dissipation factor of the cured product by containing specific carbon particles. Therefore, even if a material that increases the dielectric constant of the cured product is used, an increase in the dielectric dissipation factor can be suppressed. Therefore, the resin composition of this embodiment is also suitable as an encapsulant for electronic component devices that require a high dielectric constant and a low dielectric dissipation factor, such as AiP.

[0089] <Method for Producing Resin Composition> A method for producing a resin composition according to an embodiment of the present disclosure includes mixing a curable resin with carbon particles, wherein the carbon particles satisfy at least one of the following conditions (1) and (2): (1) a pH of 5.0 or less; and (2) an average particle diameter of 80 nm or more.

[0090] According to the above method, a resin composition having a low dielectric loss tangent of the cured product can be obtained. The method for mixing the curable resin and the carbon particles is not particularly limited. For example, a method in which the curable resin, the carbon particles, and other components that are optionally included are mixed using a mixer or the like can be used. After mixing the curable resin and the carbon particles, the mixture may be melt-kneaded, cooled, pulverized, tableted, or other steps as needed.

[0091] The resin composition produced by the above method may be the resin composition according to the embodiment of the present disclosure described above. Therefore, the details and preferred aspects of the resin composition produced by the above method may be the same as the details and preferred aspects of the resin composition according to the embodiment of the present disclosure described above.

[0092] An electronic component device according to an embodiment of the present disclosure includes a support member, an electronic component disposed on the support member, and a cured product of the 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 (e.g., 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 resin composition (e.g., a high-frequency device).

[0093] 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.

[0094] In the electronic component device of the present embodiment, 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 resin composition described above, with another resin composition, or may not be encapsulated.

[0095] (Method for manufacturing an electronic component device) The method for manufacturing an electronic component device according to this embodiment includes a step of placing electronic components on a support member and a step of encapsulating the electronic components with the resin composition described above. 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 components 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.

[0096] Methods for encapsulating electronic components using the resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is the most common.

[0097] 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.

[0098] <Preparation of Resin Compositions> Resin compositions of Examples and Comparative Examples were prepared by mixing the components shown below in the blending ratios (parts by mass) shown in Table 1. The resulting resin compositions were solid at room temperature and normal pressure. In Table 1, blank cells indicate that the component was not included.

[0099] Epoxy resin 1: orthocresol novolac type epoxy resin, epoxy equivalent weight 200 g / eq (DIC Corporation, product name "N500P-2") Epoxy resin 2: biphenyl type epoxy resin, epoxy equivalent weight 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000") Epoxy resin 3: biphenyl aralkyl type epoxy resin, epoxy equivalent weight 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")

[0100] Curing agent 1: active ester compound, manufactured by DIC Corporation, product name "EXB-8" Curing agent 2: phenol aralkyl type phenol resin, hydroxyl group equivalent 170 g / eq (manufactured by Meiwa Kasei Co., Ltd., product name "MEHC7851SS")

[0101] Curing accelerator: triphenylphosphine / 1,4-benzoquinone adduct Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573") Mold release agent: Montan acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")

[0102] Carbon particle 1: carbon black, pH: 5.8, particle size: 20 nm Carbon particle 2: carbon black, pH: 3.2, particle size: 24 nm Carbon particle 3: carbon black, pH: 4.4, particle size: 46 nm Carbon particle 4: carbon black, pH: 3.5, particle size: 133 nm Carbon particle 5: carbon black, pH: 6.4, particle size: 122 nm

[0103] Inorganic filler 1: calcium titanate particles, volume average particle diameter: 0.2 μm Inorganic filler 2: calcium titanate particles, volume average particle diameter: 15.4 μm Inorganic filler 3: alumina particles, volume average particle diameter: 7 μm

[0104] Flow aid 1: Indene coumarone resin Flow aid 2: Triphenylphosphine oxide

[0105] <Evaluation of Physical Properties of Resin Composition> (Dielectric Loss Tangent) The resin composition was charged into a vacuum hand press and molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 600 seconds. Post-curing was performed at 175°C for 6 hours to obtain a plate-shaped cured product (length 12.5 mm, width 25 mm, thickness 0.2 mm). This plate-shaped cured product was used as a test piece and the dielectric loss tangent Df at 10 GHz was measured using a dielectric constant measuring device (Agilent Technologies, product name "Network Analyzer N5227A"). The results are shown in Table 1.

[0106] (Fluidity) Using a spiral flow measurement mold conforming to EMMI-1-66, the resin composition was molded under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds, and the flow distance SF (cm) was determined. The results are shown in Table 1.

[0107] (Gel Time) Measurement was carried out at a temperature of 175° C. using a Curelastometer manufactured by JSR Trading Co., Ltd. for 3 g of the resin composition, and the time until the torque curve rose was taken as the gel time GT (seconds). The results are shown in Table 1.

[0108] (Bending Strength) The resin compositions obtained in each Example and Comparative Example were molded into 4.0 mm x 10.0 mm x 80 mm rectangular parallelepipeds using a transfer molding machine at a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. The specimens were then post-cured at 180 ° C for 5 hours to prepare test specimens for evaluating bending strength. Using these test specimens, bending tests were performed using a Tensilon universal testing machine (Instron 5948, Instron Corporation) under conditions of a support distance of 64 mm, a crosshead speed of 10 mm / min, and a temperature of 25 ° C. Using the measured results, a bending stress-displacement curve was created from equation (A), and the maximum stress was taken as the bending strength (MPa). The results are shown in Table 1.

[0109] σ=3FL / 2bh ２ Formula (A) σ: bending stress (MPa) F: bending load (N) L: distance between supports (mm) b: test piece width (mm) h: test piece thickness (mm)

[0110]

[0111] As shown in Table 1, when Examples 1 to 4, which used carbon particles 2 to 5 having a pH of 5.0 or less or a particle diameter of 80 nm or more, were compared with Comparative Example 1, which was identical to Examples 1 to 4 except that carbon particles 1 having a pH of more than 5.0 and a particle diameter of less than 80 nm were used, the values ​​of the dielectric loss tangent Df of the cured products of the resin compositions of Examples 1 to 4 were smaller than Comparative Example 1. Similarly, when Examples 5 and 6, which used carbon particles 2 and 4 having a pH of 5.0 or less or a particle diameter of 80 nm, were compared with Comparative Example 2, which was identical to Examples 5 and 6 except that carbon particles 1 having a pH of more than 5.0 and a particle diameter of less than 80 nm were used, the values ​​of the dielectric loss tangent Df of the cured products of the resin compositions of Examples 5 and 6 were smaller than Comparative Example 2.

[0112] Furthermore, in the Examples using carbon particles 2 to 5, the bending strength of the cured resin composition was greater than that of the Comparative Example using carbon particles 1. The reason for this is unclear, but it is thought that the presence of many functional groups on the surface of the carbon black improved the wettability and adhesiveness with the resin.

[0113] <Evaluation of Conductivity of Carbon Particles> In order to compare the conductivity of carbon particles 1 to 5, resin plates (cured products of epoxy resin 3 and curing agent 2) containing 10% by volume of each carbon particle were prepared, and the volume resistivity (Ω cm) was measured using the double ring electrode method in accordance with JIS K6911 (2006) and JIS K6271 (2015). The results are as follows. The volume resistivity of the resin plate not containing carbon particles was 5.8 × 10 １６ The value was Ω·cm.

[0114] Carbon particles 1: 6.6 x 10 ８ Ω・cm Carbon particle 2: 7.0×10 １２ Ω・cm Carbon particle 3: 3.6×10 １６ Ω・cm Carbon particles 4: 5.1×10 １６ Ω・cm Carbon particles 5: 3.1×10 １１ Ω cm

[0115] As described above, the volume resistivities of the resin plates containing carbon particles 2 to 5, which had a pH of 5.0 or less or an average particle size of 80 nm or more, were higher than the volume resistivity of the resin plate containing carbon particles 1, which had a pH of more than 5.0 and an average particle size of less than 80 nm. From the above, it is believed that the low electrical conductivity of carbon particles 2 to 5 is involved in the result shown in Table 1, in which the dielectric loss tangents of the cured products of the examples using carbon particles 2 to 5 were lower than those of the comparative example using carbon particle 1.

[0116] All publications, patent applications, and technical standards mentioned in this specification are incorporated by reference into this specification to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A resin composition comprising a curable resin and carbon particles, the carbon particles satisfying at least one of the following (1) and (2): (1) The pH is 5.0 or less. (2) The average particle size is 80 nm or more.

2. The resin composition according to claim 1, wherein the carbon particles satisfy at least (1).

3. The resin composition according to claim 1, wherein the carbon particles satisfy at least (2).

4. The resin composition according to claim 1, wherein the carbon particles include carbon black.

5. The resin composition according to claim 1, wherein the curable resin comprises an epoxy resin.

6. An electronic component device comprising: a support member; an electronic component placed on the support member; and a cured product of the resin composition according to any one of claims 1 to 5 that encapsulates the electronic component.

7. The electronic component device of claim 6, wherein the electronic component includes an antenna.

8. A method for producing a resin composition, comprising mixing a curable resin with carbon particles, the carbon particles satisfying at least one of the following (1) and (2): (1) The pH is 5.0 or less. (2) The average particle size is 80 nm or more.

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