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

Abstract

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

Description

Technical Field

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

[0002] In the field of wireless communication in recent years, with the increase in the number of channels and the increase in the amount of information transmitted, the high frequency of radio waves is being promoted. In the transmission loss of electrical signals used for wireless communication, the amount of loss (dielectric loss) related to insulators such as sealing materials of the circuit increases in proportion to the frequency of the radio wave, the square root of the relative dielectric constant of the insulator, and the product of the dielectric loss tangent of the insulator. Therefore, in terms of the increase in the frequency of the radio wave, from the perspective of suppressing the transmission loss of the electrical signal, the importance of reducing the relative dielectric constant or dielectric loss tangent of the insulator increases.

[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 an insulator obtained by curing the resin composition has a low dielectric loss tangent.

[0004] Patent Document 1: Japanese Patent Application Publication No. 2012-246367

[0005] Patent Document 2: Japanese Patent Application Publication No. 2014-114352 Summary of the invention

[0006] [Problems to be solved by the invention]

[0007] The cured products of the resin compositions described in Patent Documents 1 and 2 have low dielectric loss tangents, which can help reduce dielectric loss, but the amount of curing agent that can be contained in the resin composition is limited. Therefore, it is desirable to develop a technology for reducing the dielectric loss tangent of the cured product by means other than the curing agent.

[0008] The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a resin composition capable of obtaining a cured product having a low dielectric loss tangent, an electronic component device obtained using the resin composition, and a method for producing the resin composition.

[0009] [Technical means to solve the problem]

[0010] Specific means for solving the above-mentioned problems include the following aspects.

[0011] <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).

[0012] (1) pH below 5.0

[0013] (2) Average particle size is 80 nm or more

[0014] <2> The resin composition according to <1>, wherein the carbon particles satisfy at least (1).

[0015] <3> The resin composition according to <1>, wherein the carbon particles satisfy at least (2).

[0016] <4> The resin composition according to any one of <1> to <3>, wherein the carbon particles contain carbon black.

[0017] <5> The resin composition according to any one of <1> to <4>, wherein the curable resin includes an epoxy resin.

[0018] <6> An electronic component device, comprising:

[0019] Supporting members;

[0020] electronic components, disposed on the supporting member; and

[0021] A cured product of the resin composition according to any one of <1> to <5> for sealing the electronic component.

[0022] <7> The electronic component device according to <6>, wherein the electronic component includes an antenna.

[0023] <8> A method for producing a resin composition, comprising mixing a curable resin and carbon particles, wherein the carbon particles satisfy at least one of the following (1) and (2).

[0024] (1) pH below 5.0

[0025] (2) Average particle size is 80 nm or more

[0026] [Effects of the Invention]

[0027] According to the present disclosure, there are provided a resin composition capable of obtaining a cured product having a low dielectric loss tangent, an electronic component device obtained using the resin composition, and a method for producing the resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] none DETAILED DESCRIPTION

[0029] In the present disclosure, the term "process" includes processes that are independent of other processes and processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved.

[0030] In the present disclosure, in a numerical range represented by “to”, numerical values ​​described before and after including “to” are respectively regarded as the minimum value and the maximum value.

[0031] In the numerical range recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range may also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in the present disclosure, the upper limit or lower limit of the numerical range may also be replaced by the value shown in the embodiment.

[0032] In the present disclosure, each component may include a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the plurality of substances present in the composition.

[0033] In the present disclosure, multiple types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to the value for the mixture of the multiple types of particles present in the composition unless otherwise specified.

[0034] Hereinafter, the form for implementing the present disclosure is described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, its constituent parts (including component processes, etc.) are not necessary except for the cases specifically indicated. The same is true for numerical values ​​and their ranges, and the present disclosure is not limited.

[0035] <Resin composition>

[0036] 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).

[0037] (1) pH below 5.0

[0038] (2) Average particle size is 80 nm or more

[0039] A resin composition used for sealing electronic components may contain carbon particles such as carbon black for the purpose of coloring, light shielding, laser marking assistance, etc.

[0040] Since carbon particles are generally conductive, it is considered that they are one factor that increases the dielectric loss tangent of the cured product.

[0041] In the present embodiment, the carbon particles contained in the resin composition satisfy at least one of (1) and (2). This is considered to contribute to lowering the dielectric loss tangent of the cured product of the resin composition.

[0042] Hereinafter, each component constituting the resin composition will be described. The resin composition of the present embodiment contains a curable resin and carbon particles, and may contain other components as necessary.

[0043] (Carbon particles)

[0044] The resin composition in this embodiment contains carbon particles.

[0045] In the present disclosure, the carbon particles refer to particulate substances in which 90 mass % or more of all elements are carbon.

[0046] Examples of the 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.

[0047] The type of carbon black is not particularly limited and can be selected according to the desired properties. Carbon black can be selected from furnace black, channel black, acetylene black, thermal black, and the like, for example.

[0048] The carbon particles contained in the resin composition may be only one kind or two or more kinds.

[0049] From the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition, the pH of the carbon particles is preferably 5.0 or less.

[0050] Regarding carbon particles with a pH of 5.0 or less, it is believed that the amount of polar groups such as carboxyl groups contained in the carbon particles is relatively large, and the electron migration between the carbon particles is easily hindered by the polar groups (which may also be in a state of reaction with the components in the resin composition). As a result, it is believed that the dielectric loss tangent of the cured product of the resin composition containing the carbon particles is reduced.

[0051] The pH of the carbon particles is more preferably 4.5 or less, and further preferably 4.0 or less.

[0052] From the viewpoint of preventing corrosion of metal members such as metal wires, the pH of the carbon particles is preferably 3.0 or higher.

[0053] In the present disclosure, the pH of carbon particles is a value measured at 25° C. and is measured by the boiling extraction method specified in Japanese Industrial Standards (JIS) K5101-17-1 (2004).

[0054] From the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition, the average particle diameter of the carbon particles is preferably 80 nm or more.

[0055] Carbon particles having an average particle size of 80 nm or more are believed to have a relatively small specific surface area and thus electron migration between carbon particles is less likely to occur. As a result, the dielectric loss tangent of the cured product of the resin composition containing the carbon particles is believed to decrease.

[0056] The average particle size of the carbon particles is more preferably 90 nm or more, and further preferably 100 nm or more.

[0057] 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.

[0058] In the present disclosure, the average particle size of carbon particles is measured by image analysis.

[0059] The method of image analysis is not particularly limited. For example, a method of observing carbon particles using an optical microscope or an electron microscope can be cited. The counting of carbon particles can be performed visually or using an image analysis system.

[0060] From the viewpoint of measurement accuracy, the image analysis is performed under the conditions that the total number of carbon particles to be measured is 100 or more and the observation magnification is 1000 times or more.

[0061] The arithmetic mean of the particle diameters of the carbon particles to be measured is defined as the average particle diameter of the carbon particles.

[0062] The particle size of the carbon particles to be measured is defined as the equivalent circle diameter of the observed particles.

[0063] When the carbon particles form aggregates, the particle size of the carbon particles is defined as the particle size of the particles (primary particles) forming the aggregates.

[0064] The content of the carbon particles contained in the resin composition is not particularly limited.

[0065] From the viewpoint of achieving the desired purpose such as coloring, the content of the carbon particles is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, based on the entire resin composition.

[0066] From the viewpoint of suppressing the dielectric loss tangent of the cured product to be low, the content of the carbon particles is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the entire resin composition.

[0067] (hardening resin)

[0068] The resin composition in this embodiment contains a curable resin.

[0069] The curable resin may be any of a thermosetting resin and a photocurable resin, but is preferably a thermosetting resin from the viewpoint of mass productivity.

[0070] Examples of the thermosetting resin include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, polyimide resins such as bismaleimide resins, polyamide resins, polyamideimide resins, silicone resins, acrylic resins, etc. From the viewpoint of formability 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 epoxy resins.

[0071] The resin composition may contain only one type of curable resin, or may contain two or more types.

[0072] Hereinafter, epoxy resin will be described as an example of curable resin.

[0073] -Epoxy resin-

[0074] The resin composition preferably contains an epoxy resin as a curable resin.

[0075] When the resin composition contains an epoxy resin as the curable resin, the content of the epoxy resin relative to the entire 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.

[0076] The type of the epoxy resin is not particularly limited as long as it is a compound having an epoxy group in the molecule.

[0077] Specific examples of epoxy resins include: novolac-type epoxy resins (phenol novolac-type epoxy resins, o-cresol novolac-type epoxy resins, etc.) 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, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolac resin, and then epoxidizing the novolac resin; and triphenylmethane-type phenol resins obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst, and then epoxidizing the triphenylmethane-type phenol resins. triphenylmethane epoxy resin obtained by epoxidizing a phenol resin; a copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound under an acidic catalyst; a diphenylmethane epoxy resin as a diglycidyl ether of bisphenol A, bisphenol F, etc.; a biphenyl epoxy resin as a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a styrene epoxy resin as a diglycidyl ether of a styrene-based phenol compound; an epoxy resin containing sulfur atoms as a diglycidyl ether of bisphenol S, etc.; an epoxy resin as a glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; an epoxy resin as a diglycidyl ether of phthalic acid, isophthalic acid, glycidyl ester epoxy resins of glycidyl esters of polycarboxylic acid compounds such as phthalic acid and tetrahydrophthalic acid; glycidylamine epoxy resins obtained by replacing the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with a glycidyl group; dicyclopentadiene epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; alicyclic epoxy resins such as diepoxy vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. obtained by epoxidizing an olefin bond in the molecule; glycidyl ethers as p-xylene-modified phenol resins p-xylene modified epoxy resin; meta-xylene modified epoxy resin as glycidyl ether of meta-xylene modified phenol resin; terpene modified epoxy resin as glycidyl ether of terpene modified phenol resin; dicyclopentadiene modified epoxy resin as glycidyl ether of dicyclopentadiene modified phenol resin; cyclopentadiene modified epoxy resin as glycidyl ether of cyclopentadiene modified phenol resin; polycyclic aromatic ring modified epoxy resin as glycidyl ether of polycyclic aromatic ring modified phenol resin; naphthalene type epoxy resin as glycidyl ether of phenol resin containing naphthalene ring; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bonds using peracids such as peracetic acid;Aralkyl epoxy resins obtained by epoxidizing aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins. Furthermore, epoxides of acrylic resins and the like can also be cited as epoxy resins. These epoxy resins can be used alone or in combination of two or more. ;

[0078] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balancing 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.

[0079] The epoxy equivalent of the epoxy resin is set to a value measured by a method in accordance with Japanese Industrial Standards (JIS) K 7236:2009.

[0080] When the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and reflow resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C, and from the viewpoint of operability during preparation of the resin composition, it is more preferably 50°C to 130°C.

[0081] The melting point or softening point of the epoxy resin is defined as a value measured by differential scanning calorimetry (DSC) or a method (ring and ball method) in accordance with JIS K 7234: 1986.

[0082] When the resin composition contains an epoxy resin as a curable resin, the mass ratio 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 further preferably 3.5 mass % to 13 mass %, from the viewpoints of strength, fluidity, heat resistance, formability, etc.

[0083] - Hardener -

[0084] When the resin composition contains an epoxy resin as a curable resin, the resin composition may further contain a curing agent.

[0085] From the viewpoint of reducing the dielectric loss tangent of the hardened material, the resin composition preferably contains an active ester compound as a hardener. One active ester compound can be used alone or in combination of two or more. Here, the active ester compound refers to a compound having one or more ester groups that react with an epoxy group in one molecule and having a hardening effect of an epoxy resin. In addition, when the hardener contains an active ester compound, the hardener may contain a hardener other than the active ester compound, or may not contain a hardener other than the active ester compound.

[0086] When an active ester compound is used as a curing agent, the dielectric loss tangent of the cured product can be suppressed to be low compared to the case of using other curing agents (for example, a phenol curing agent). The reason for this is presumably as follows.

[0087] In the reaction between epoxy resin and phenol hardener, secondary hydroxyl groups are generated. In contrast, in the reaction between epoxy resin and active ester compound, ester groups are generated instead of secondary hydroxyl groups. Since ester groups have lower polarity than secondary hydroxyl groups, the resin composition containing active ester compound as hardener can suppress the dielectric loss tangent of hardened material to be lower than the resin composition containing only hardener that generates secondary hydroxyl groups as hardener.

[0088] In addition, the polar groups in the cured product increase the water absorption of the cured product. By using an active ester compound as a curing agent, the concentration of polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. Furthermore, by suppressing the water absorption of the cured product, that is, suppressing the H as a polar molecule 2 The content of O can suppress the dielectric loss tangent of the cured product to a lower level.

[0089] The type of active ester compound is not particularly limited as long as it has one or more ester groups that react with epoxy groups in the molecule. Examples of active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esters of heterocyclic hydroxy compounds.

[0090] Examples of the active ester compound 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 hydroxyl compound and an aromatic hydroxyl compound. An ester compound using an aliphatic compound as a polycondensation component tends to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain. An ester compound using an aromatic compound as a polycondensation component tends to have excellent heat resistance due to the presence of an aromatic ring.

[0091] As specific examples of active ester compounds, aromatic esters obtained by condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups can be cited. Among them, aromatic carboxylic acid components obtained by replacing 2 to 4 hydrogen atoms of aromatic rings such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfonic acid with carboxyl groups, monohydric phenols obtained by replacing 1 hydrogen atom of the aromatic ring with hydroxyl groups, and mixtures of polyhydric phenols obtained by replacing 2 to 4 hydrogen atoms of the aromatic ring with hydroxyl groups as raw materials are preferably used. Aromatic esters obtained by condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups. That is, aromatic esters having structural units derived from the aromatic carboxylic acid components, structural units derived from the monohydric phenols, and structural units derived from the polyhydric phenols are preferably used.

[0092] Specific examples of active ester compounds include phenol resins having a molecular structure in which a phenol compound is linked via an aliphatic cyclic hydrocarbon group, as described in Japanese Patent Laid-Open No. 2012-246367, and active ester resins having a structure obtained by reacting an aromatic dicarboxylic acid or a halide thereof with an aromatic monohydroxy compound. The active ester resin is preferably a compound represented by the following structural formula (1).

[0093] [Chemistry 1]

[0094]

[0095] In the structural formula (1), R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, X is 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 is 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.

[0096] Specific examples of the compound represented by the structural formula (1) include the following exemplary compounds (1-1) to (1-10): t-Bu in the structural formula is a tert-butyl group.

[0097] [Chemistry 2]

[0098]

[0099] [Chemistry 3]

[0100]

[0101] 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) described in JP-A-2014-114352.

[0102] [Chemistry 4]

[0103]

[0104] In the 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 site (z1) or a hydrogen atom (z2) 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, and at least one of Z is an ester-forming structural site (z1).

[0105] In the 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 site (z1) or a hydrogen atom (z2) 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, and at least one of Z is an ester-forming structural site (z1).

[0106] Specific examples of the compound represented by the structural formula (2) include the following exemplary compounds (2-1) to (2-6).

[0107] [Chemistry 5]

[0108]

[0109] Specific examples of the compound represented by the structural formula (3) include the following exemplary compounds (3-1) to (3-6).

[0110] [Chemistry 6]

[0111]

[0112] As the active ester compound, commercially available products can also be used. As commercially available products of the active ester compound, the active ester compound containing a dicyclopentadiene type diphenol structure can be listed as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Corporation); the active ester compound containing an aromatic structure can be listed as "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Corporation); the active ester compound containing an acetylated product of phenol novolac can be listed as "DC808" (manufactured by Mitsubishi Chemical Corporation); the active ester compound containing a benzoylated product of phenol novolac can be listed as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), etc.

[0113] The ester equivalent (molecular weight / number of ester groups) of the active ester compound is not particularly limited, but 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 from the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability.

[0114] The ester equivalent of the active ester compound is set to a value measured by a method in accordance with JIS K 0070:1992.

[0115] The hardener may also contain other hardeners other than the active ester compound. The type of other hardener is not particularly limited and can be selected according to the desired properties of the resin composition. Examples of other hardeners include phenol hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, and the like.

[0116] Specific examples of the phenol curing agent include: polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde in the presence of an acid catalyst; and polyphenol compounds such as polyphenols obtained by condensing or co-condensing the phenolic compounds with dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, and the like. Synthetic aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; p-xylene-modified phenol resins and m-xylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; dicyclopentadiene-type phenol resins and dicyclopentadiene-type naphthol resins synthesized by copolymerizing the above-mentioned phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these, etc. These phenolic hardeners may be used alone or in combination of two or more.

[0117] The functional group equivalent weight (hydroxyl group equivalent weight in the case of phenolic hardener) of the other hardener is not particularly limited. From the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability, the functional group equivalent weight of the other hardener is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0118] The functional group equivalent of other curing agents (hydroxyl group equivalent in the case of a phenol curing agent) is set to a value measured by a method in accordance with JISK 0070:1992.

[0119] 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 workability during production of the resin composition, more preferably 50°C to 130°C.

[0120] The melting point or softening point of the curing agent is set to a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0121] The equivalent ratio of epoxy resin to hardener (all hardeners when multiple hardeners are used), that is, the ratio of the number of functional groups in the hardener to the number of functional groups in the epoxy resin (number of functional groups in the hardener / number of functional groups in the epoxy resin) is not particularly limited. From the perspective of suppressing the respective unreacted components to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the perspective of formability and reflow resistance, it is further preferably set in the range of 0.8 to 1.2.

[0122] When the hardener includes an active ester compound and other hardeners, from the viewpoint of suppressing the dielectric loss tangent of the hardened material to a low level, the mass ratio of the active ester compound in the total amount of the active ester compound and other hardeners is preferably 40 mass % or more, more preferably 50 mass % or more, and even more preferably 60 mass % or more.

[0123] (hardening accelerator)

[0124] The resin composition may also contain a hardening accelerator. The type of the hardening accelerator is not particularly limited, and can be selected according to the type of the curable resin, the desired properties of the resin composition, and the like.

[0125] 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 a curable resin include diazabicycloolefins 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 2-heptadecylimidazole. Cyclic amidine compounds; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; compounds having intramolecular polarization formed by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, compounds having π bonds such as diazonophenylmethane and the like to these compounds; tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, tetraphenylborate of N-methylmorpholine and the like amidinium compounds; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the 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; first phosphines such as ethylphosphine and phenylphosphine, second phosphines such as dimethylphosphine and diphenylphosphine, triphenylphosphine, diphenyl(p-toluene)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl-alkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine )phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tri(benzyl)phosphine and other tertiary phosphine; phosphine compounds such as complexes of the above-mentioned organic phosphine and organic boron; compounds with intramolecular polarization formed by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone and other quinone compounds, diazonophenylmethane and other compounds having π bonds to the above-mentioned organic phosphine or the above-mentioned phosphine compound;The organic phosphine or the phosphine compound is reacted with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 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-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6- Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as bromo-2-naphthol and 4-bromo-4'-hydroxybiphenyl and then undergoing a dehydrohalogenation process; tetraphenyl phosphonium and other tetrasubstituted phosphoniums, tetraphenyl phosphonium tetra-p-toluene borate and other tetraphenyl borate salts of tetrasubstituted phosphoniums; tetrasubstituted phosphonium compounds such as salts of tetrasubstituted phosphoniums and phenol compounds; salts of tetraalkyl phosphoniums and partial hydrolyzates of aromatic carboxylic anhydrides; phosphate betaine compounds; adducts of phosphonium compounds and silane compounds, etc. ;

[0126] The hardening accelerator may be used alone or in combination of two or more.

[0127] Among these, the curing accelerator is preferably a curing accelerator containing an organic phosphine. Examples of the curing accelerator containing an organic phosphine include phosphine compounds such as the organic phosphine and complexes of the organic phosphine and organic boron, and compounds having intramolecular polarization formed by adding a compound having a π bond to the organic phosphine or the phosphine compound.

[0128] Among these, particularly preferred hardening 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.

[0129] When the resin composition contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the resin component (the total amount of the hardening resin and the hardening agent included as needed, the same below). If the amount of the hardening accelerator is 0.1 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to cure well in a short time. If the amount of the hardening accelerator is 30 parts by mass or less relative to 100 parts by mass of the resin component, there is a tendency to obtain a good molded product whose hardening speed is not too fast.

[0130] (Inorganic filler)

[0131] The resin composition may contain an inorganic filler.

[0132] Specific examples of the inorganic filler include crystalline silica, fused silica, alumina, calcium titanate, barium titanate, glass, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, mica and other inorganic materials.

[0133] The resin composition may also contain an inorganic filler having a flame retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

[0134] The inorganic filler may be used alone or in combination of two or more.

[0135] From the viewpoint of improving the thermal conductivity of the cured product, the resin composition preferably contains alumina particles as an inorganic filler.

[0136] From the viewpoint of increasing the relative dielectric constant of the cured product, the resin composition preferably contains at least one selected from the group consisting of calcium titanate particles and barium titanate particles as an inorganic filler. From the viewpoint of increasing the relative dielectric constant of the cured product and reducing the dielectric loss tangent, the resin composition preferably contains calcium titanate particles as an inorganic filler.

[0137] The inorganic filler that increases the relative dielectric constant of the cured product is suitable, for example, when the resin composition is used for production of an antenna system package type electronic component device described later.

[0138] When the resin composition contains alumina particles, the content of the alumina particles is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 50 to 70% by mass based on the entire inorganic filler.

[0139] 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 the barium titanate particles is preferably 10% to 60% by mass, more preferably 20% to 50% by mass, and even more preferably 30% to 40% by mass based on the entire inorganic filler.

[0140] 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.

[0141] The resin composition may contain two or more inorganic fillers having different volume average particle sizes.

[0142] The volume average particle size of the inorganic filler is defined as a particle size at which the cumulative value of the particle size distribution obtained by laser diffraction / scattering is 50% (volume basis). The particle size distribution is measured, for example, as follows.

[0143] First, an inorganic filler was added to a dispersion medium (water) in a range of 0.01 mass % to 0.1 mass %, and dispersed for 5 minutes using a bath type ultrasonic cleaning machine. Then, 5 ml of the obtained dispersion was injected into a tank, and the particle size distribution was measured at 25° C. using a laser diffraction / scattering particle size distribution measuring device (Horiba Manufacturing Co., Ltd., LA920).

[0144] The content of the inorganic filler is preferably 40% to 90% by volume, more preferably 50% to 85% by volume, and still more preferably 60% to 80% by volume, based on the entire resin composition.

[0145] When the composition of the resin composition is known, the content (volume %) of the inorganic filler in the resin composition can be calculated based on 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 calculated by the following method.

[0146] A thin slice sample of a cured product of the resin composition is photographed using a scanning electron microscope (SEM). An arbitrary area S is determined in the SEM image, and the total area A of the inorganic filler contained in the area S is calculated. The value obtained by dividing the total area A of the inorganic filler by the area S is converted into a percentage (%), and the value is set as the content (volume %) of the inorganic filler in the resin composition.

[0147] The area S is set to be sufficiently large relative to the size of the inorganic filler. For example, it is set to be large enough to contain 100 or more inorganic fillers. The area S may also be the total of a plurality of cut surfaces.

[0148] The inorganic filler may have a ratio deviation in the gravity direction when the resin composition is cured. In such a case, when photographing with SEM, the entire cured product in the gravity direction is photographed, and the area S including the entire cured product in the gravity direction is determined.

[0149] [Various additives]

[0150] In addition to the above components, the resin composition may also contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, stress relaxants, and fluidity imparting agents exemplified below. In addition to the additives exemplified below, the resin composition may also contain various additives known in the art as needed.

[0151] (Coupling agent)

[0152] The resin composition may also contain a coupling agent. The coupling agent is not particularly limited, and a previously known coupling agent can be used. Specifically, silane compounds such as epoxy silane, mercapto silane, amino silane, ureide silane, vinyl silane, disilazane, titanium compounds, aluminum chelate compounds, aluminum / zirconium compounds, etc. can be cited.

[0153] When the resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass, based on 100 parts by mass of the inorganic filler.

[0154] (Ion Exchanger)

[0155] The resin composition may also contain an ion exchanger. There is no particular limitation on the ion exchanger, and previously known ion exchangers may be used. Specifically, hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth may be cited. The ion exchangers may be used alone or in combination of two or more. Among them, the hydrotalcite represented by the following general formula (A) is preferred.

[0156] Mg (1-X) Al X (OH) 2 (CO 3 ) X / 2 ·mH 2 O……(A)

[0157] (0<X≦0.5, m is a positive number)

[0158] When the resin composition contains an ion exchanger, the content of the ion exchanger is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin component.

[0159] (Release Agent)

[0160] The resin composition may also contain a release agent. There is no particular limitation on the release agent, and any known release agent may be used. Specifically, examples include: palm wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. The release agent may be used alone or in combination of two or more.

[0161] When the resin composition contains a release agent, the amount of the release agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin component.

[0162] (Flame Retardant)

[0163] The resin composition may also contain a flame retardant. The flame retardant is not particularly limited, and a previously known flame retardant may be used. Specifically, organic compounds or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. may be mentioned. The flame retardant may be used alone or in combination of two or more.

[0164] When the resin composition contains a flame retardant, the amount of the flame retardant is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the resin component.

[0165] (Stress Relief Agent)

[0166] The resin composition may also contain a stress relaxant. By including a stress relaxant in the resin composition, the warping deformation of the package and the generation of package cracks can be further reduced. As a stress relaxant, commonly used known stress relaxants (flexible agents) can be listed. Specifically, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene can be listed; rubber particles such as natural rubber (natural rubber, NR), acrylonitrile butadiene rubber (acrylonitrile butadiene rubber, NBR), acrylic rubber, urethane rubber, and silicone powder; methyl methacrylate-styrene-butadiene copolymer (methacrylate methyl styrenebutadiene, MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. have a core-shell structure. The stress relaxant can be used alone or in combination of two or more.

[0167] Among the stress relaxants, silicone-based stress relaxants are preferred. Examples of silicone-based stress relaxants include silicone-based stress relaxants having epoxy groups, silicone-based stress relaxants having amino groups, silicone-based stress relaxants obtained by polyether-modifying these, and silicone compounds such as silicone compounds having epoxy groups and polyether silicone compounds are more preferred.

[0168] When the resin composition contains a stress relaxant, the amount of the stress relaxant is, for example, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the resin component.

[0169] (Flowability Imparting Agent)

[0170] The resin composition may contain a fluidity-imparting agent. Specific examples of the fluidity-imparting agent include indene-coumarone resin and triphenylphosphine oxide.

[0171] 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, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the resin component.

[0172] The resin composition is preferably solid at room temperature and pressure (e.g., 25° C., atmospheric pressure). The shape of the resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, and sheets. From the perspective of operability, the size and mass of the resin composition when it is in sheet form are preferably the size and mass that match the molding conditions of the package.

[0173] (Physical Properties of Resin Composition)

[0174] The resin composition is formed by compression molding under the conditions of a mold temperature of 175°C, a molding pressure of 6.9MPa, and a curing time of 600 seconds to obtain a cured product, and the dielectric loss tangent of the cured product at 10GHz obtained can be, for example, 0.020 or less. From the perspective of reducing transmission loss, the dielectric loss tangent of the cured product at 10GHz is preferably 0.018 or less, more preferably 0.015 or less, and further preferably 0.010 or less. The lower limit of the dielectric loss tangent of the cured product at 10GHz is not particularly limited, and for example, 0.004 can be cited.

[0175] The dielectric loss tangent was measured by the method described in Examples.

[0176] Using the spiral flow measurement mold according to the Epoxy Molding Material Institute (EMMI)-1-66, the resin composition is formed under the conditions of a mold temperature of 175°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and the flow distance at this time is preferably 60cm or more, more preferably 70cm or more, and further preferably 80cm or more. Hereinafter, the flow distance is also referred to as "spiral flow". The upper limit of the spiral flow is not particularly limited, and for example, 200cm can be cited.

[0177] The spiral flow was measured by the method described in the Examples.

[0178] The gel time of the resin composition at 175° C. is preferably 30 seconds or more to 100 seconds, more preferably 40 seconds to 70 seconds.

[0179] The gel time of the resin composition at 175° C. was measured as follows. Specifically, 3 g of a sample of the resin composition was measured at 175° C. using a curelastometer manufactured by JSR Trading Co., Ltd., and the time until the torque curve rose was defined as the gel time (sec).

[0180] The gel time was measured by the method described in the Examples.

[0181] (Application of resin composition)

[0182] The resin composition of this embodiment can obtain a cured product having a reduced dielectric loss tangent. Therefore, the resin composition of this embodiment is suitable as a sealing material for electronic component devices that use high-frequency radio waves for communication.

[0183] Regarding electronic components that use high-frequency radio waves in communications, the development of antenna system packages (Antenna in Package, AiP) as packages with antenna functions is also being promoted. In AiP, in order to cope with the increase in the number of channels accompanying the diversification of information, the radio waves used in communications are becoming more high-frequency, and the sealing material is required to have both a high relative dielectric constant and a low dielectric loss tangent.

[0184] The material (that is, the material with high relative dielectric constant) of the hardener of the resin composition generally has the tendency of also improving the dielectric loss tangent of the hardener. The resin composition in the present embodiment can reduce the dielectric loss tangent of the hardener by comprising specific carbon particles. Therefore, even if the material with high relative dielectric constant of the hardener is used, the rise of dielectric loss tangent can be suppressed. Therefore, the resin composition in the present embodiment is also suitable as the sealing material of the electronic component device with high relative dielectric constant and low dielectric loss tangent required by AiP and the like.

[0185] <Method for producing resin composition>

[0186] A method for producing a resin composition according to one embodiment of the present disclosure includes mixing a curable resin and carbon particles that satisfy at least one of the following (1) and (2).

[0187] (1) pH below 5.0

[0188] (2) Average particle size is 80 nm or more

[0189] According to the above method, a resin composition having a low dielectric loss tangent of a cured product can be obtained.

[0190] The method for mixing the curable resin and the carbon particles is not particularly limited, and an example thereof includes a method of mixing the curable resin, the carbon particles, and other components as required using a mixer or the like.

[0191] After the curable resin and the carbon particles are mixed, the mixture may be subjected to steps such as melt kneading, cooling, pulverization, and tableting, as necessary.

[0192] The resin composition produced in the method may be the resin composition of one embodiment of the present disclosure. Therefore, the details and preferred embodiments of the resin composition produced in the method may be the same as the details and preferred embodiments of the resin composition of one embodiment of the present disclosure.

[0193] <Electronic components and devices>

[0194] An electronic component device according to one embodiment of the present disclosure includes a supporting member, an electronic component disposed on the supporting member, and a cured product of the resin composition that seals the electronic component.

[0195] Examples of electronic component devices include those in which electronic components (active components such as semiconductor chips, transistors, diodes, thyristors, etc., passive components such as capacitors, resistors, coils, antennas, etc.) are mounted on support members such as lead frames, conveyor tapes with completed wiring, wiring boards, glass, silicon wafers, organic substrates, and the electronic component region is sealed with a resin composition (e.g., high-frequency devices).

[0196] The type of the supporting member is not particularly limited, and a supporting member generally used in the manufacture of electronic component devices can be used.

[0197] 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.

[0198] In the electronic component device of this embodiment, other electronic components may be arranged on the surface of the support member opposite to the surface on which the electronic components are arranged, if necessary. Other electronic components may be sealed with the resin composition, or may be sealed with other resin compositions, or may not be sealed.

[0199] (Method for manufacturing electronic component device)

[0200] The method for manufacturing an electronic component device according to the present embodiment includes: a step of placing an electronic component on a supporting member; and a step of sealing the electronic component with the resin composition.

[0201] The method for implementing each of the steps is not particularly limited, and can be carried out by a general method. In addition, the types of support members and electronic components used in the manufacture of electronic component devices are not particularly limited, and support members and electronic components commonly used in the manufacture of electronic component devices can be used.

[0202] Examples of methods for sealing electronic components using the resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is generally used.

[0203] [Example]

[0204] Hereinafter, the embodiment will be described in detail by way of examples, but the scope of the embodiment is not limited to these examples.

[0205] <Preparation of resin composition>

[0206] The resin compositions of Examples and Comparative Examples were prepared by mixing the following components at the blending ratios (parts by mass) shown in Table 1. The obtained resin compositions were solid at normal temperature and pressure.

[0207] In Table 1, blank columns mean that the components are not contained.

[0208] Epoxy resin 1: o-cresol novolac type epoxy resin, epoxy equivalent 200 g / eq (DIC Corporation, product name "N500P-2")

[0209] Epoxy resin 2: biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Co., Ltd., product name "YX-4000")

[0210] Epoxy resin 3: biphenyl aralkyl type epoxy resin, epoxy equivalent 274g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")

[0211] Hardener 1: Active ester compound, DIC Corporation, product name "EXB-8"

[0212] Hardener 2: Phenol aralkyl type phenol resin, hydroxyl equivalent 170 g / eq (Meiwa Chemical Co., Ltd., product name "MEHC7851SS")

[0213] Hardening accelerator: triphenylphosphine / 1,4-benzoquinone adduct

[0214] Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")

[0215] Release agent: montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")

[0216] Carbon particles 1: carbon black, pH: 5.8, particle size: 20 nm

[0217] Carbon particles 2: carbon black, pH: 3.2, particle size: 24 nm

[0218] Carbon particles 3: carbon black, pH: 4.4, particle size: 46 nm

[0219] Carbon particles 4: carbon black, pH: 3.5, particle size: 133 nm

[0220] Carbon particles 5: carbon black, pH: 6.4, particle size: 122nm

[0221] Inorganic filler 1: calcium titanate particles, volume average particle size: 0.2 μm

[0222] Inorganic filler 2: calcium titanate particles, volume average particle size: 15.4 μm

[0223] Inorganic filler 3: Alumina particles, volume average particle size: 7 μm

[0224] ·Flowability aid 1: indene-coumarone resin

[0225] ·Flowability aid 2: triphenylphosphine oxide

[0226] <Evaluation of physical properties of resin composition>

[0227] (Dielectric loss tangent)

[0228] The resin composition was placed in a vacuum manual press, 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, and cured at 175°C for 6 hours to obtain a plate-shaped cured product (12.5 mm in length, 25 mm in width, and 0.2 mm in thickness). The plate-shaped cured product was used as a test piece, and a dielectric constant measuring device (Agilent Technologies, product name "Network Analyzer N5227A") was used to measure the dielectric loss tangent Df at a temperature of 25°C ± 3°C and 10 GHz. The results are shown in Table 1.

[0229] (Liquidity)

[0230] The resin composition was molded using a spiral flow measurement mold in accordance with EMMI-1-66 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.

[0231] (Gel time)

[0232] The resin composition 3 g was measured at a temperature of 175° C. using a vulcanization tester manufactured by JSR Trading Co., Ltd., and the time until the torque curve rose was defined as the gel time GT (seconds).

[0233] (Bending Strength)

[0234] The resin composition obtained in each embodiment and each comparative example was formed into a 4.0mm×10.0mm×80mm cuboid at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds by a transfer molding machine, and hardened at 180°C for 5 hours to prepare a test piece for bending strength evaluation. Using the test piece, a bending test was performed using a Tenstron universal material testing machine (Instron 5948, Instron) at a distance of 64mm between fulcrums, a crosshead speed of 10mm / min, and a temperature of 25°C. Using the measured results, a bending stress-displacement curve was prepared according to formula (A), and its maximum stress was used as the bending strength (MPa). The results are shown in Table 1.

[0235] σ=3FL / 2bh 2 Formula (A)

[0236] σ: Bending stress (MPa)

[0237] F: Bending load (N)

[0238] L: Distance between pivot points (mm)

[0239] b: Test piece width (mm)

[0240] h: Test piece thickness (mm)

[0241] [Table 1]

[0242] Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 2 Example 5 Example 6 Epoxy resin 1 70.1 70.1 70.1 70.1 70.1 Epoxy Resin 2 30 30 30 30 30 30 30 30 Epoxy Resin 3 70.1 70.1 70.1 Hardener 1 106 106 106 106 106 51.7 51.7 51.7 Hardener 2 32.8 32.8 32.8 Hardening accelerator 5 5 5 5 5 3 3 3 Coupling agent 5 5 5 5 5 5 5 5 Release agent 1 1 1 1 1 1 1 1 Carbon particles 1 5.3 5.3 Carbon particles 2 5.3 5.3 Carbon particles 3 5.3 Carbon particles 4 5.3 5.3 Carbon particles 5 5.3 Flowability aid 1 10 10 10 10 10 10 10 10 Flowability aid 2 5 5 5 5 5 5 5 5 Filler content (Vf) 73 73 73 73 73 73 73 73 Inorganic filler 1 223 223 223 223 223 201 201 201 Inorganic filler 2 558 558 558 558 558 504 504 504 Inorganic filler 3 1378 1378 1378 1378 1378 1244 1244 1244 total 2396.4 2396.4 2396.4 2396.4 2396.4 2162.9 2162.9 2162.9 SF[cm] 69 100 90 80 75 55 73 67 GT[s] 60 60 50 60 60 47 50 47 Df 0.0057 0.0052 0.0047 0.0051 0.0053 0.0072 0.0068 0.0064 Bending Strength 116 137 125 125 120 103 120 109

[0243] As shown in Table 1, when Examples 1 to 4 using carbon particles 2 to 5 having a pH of less than 5.0 or a particle size of 80 nm or more are compared with Comparative Example 1 having the same conditions as Examples 1 to 4 except that carbon particles 1 having a pH of more than 5.0 and a particle size of less than 80 nm are used, the dielectric loss tangent Df value of the cured product of the resin composition of Examples 1 to 4 is smaller than that of Comparative Example 1.

[0244] Similarly, if Example 5 and Example 6 using carbon particles 2 and carbon particles 4 with a pH of less than 5.0 or a particle size of 80 nm or more are compared with Comparative Example 2 which has the same conditions as Example 5 and Example 6 except that carbon particles 1 with a pH of more than 5.0 and a particle size of less than 80 nm are used, the dielectric loss tangent Df value of the cured resin composition of Example 5 and Example 6 is smaller than that of Comparative Example 2.

[0245] Furthermore, in the examples using carbon particles 2 to 5, the bending strength of the cured product of the resin composition was greater than that of the comparative example using carbon particle 1. The reason for this is not clear, but it is believed that the presence of a large number of functional groups on the surface of carbon black improves wettability and adhesion to the resin.

[0246] <Evaluation of electrical conductivity of carbon particles>

[0247] In order to compare the conductivity of carbon particles 1 to 5, resin plates (cured products of epoxy resin 3 and hardener 2) containing 10 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).

[0248] The results are shown below. The volume resistivity of the resin plate without carbon particles was 5.8×10 16 Ω·cm.

[0249] Carbon particles 1: 6.6×10 8 Ω·cm

[0250] Carbon particles 2: 7.0×10 12 Ω·cm

[0251] Carbon particles 3: 3.6×10 16 Ω·cm

[0252] Carbon particles 4: 5.1×10 16 Ω·cm

[0253] Carbon particles 5: 3.1×10 11 Ω·cm

[0254] As described above, the volume resistivity of the resin plate containing carbon particles 2 to 5 having a pH of 5.0 or less or an average particle size of 80 nm or more is greater than the volume resistivity of the resin plate containing carbon particles 1 having a pH of more than 5.0 and an average particle size of less than 80 nm.

[0255] Based on the above, the results shown in Table 1 that the dielectric loss tangent of the cured products of the examples using carbon particles 2 to 5 is lower than that of the comparative example using carbon particles 1 are considered to be related to the low conductivity of carbon particles 2 to 5.

[0256] All documents, patent applications, and technical specifications described in this specification are incorporated herein by reference to the same extent as if each document, patent application, or technical specification was specifically and individually described as being incorporated by reference.

Claims

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) pH below 5.0 (2) The average particle size is 80 nm or more.

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

3. The resin composition according to claim 1, wherein The carbon particles at least satisfy (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 hardening resin includes epoxy resin.

6. An electronic component device comprising: Supporting members; Electronic components are arranged on the supporting member; as well as A cured product of the resin composition according to any one of claims 1 to 5, which seals the electronic component.

7. The electronic component device according to 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, wherein the carbon particles satisfy at least one of the following (1) and (2); (1) pH below 5.0 (2) The average particle size is 80 nm or more.

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