Resin composition for molding and electronic component device

Abstract

To provide a resin composition for molding which is excellent in laser workability.SOLUTION: A resin composition for molding contains a curable resin, an inorganic filler containing a titanium-containing high dielectric filler, carbon black, and a black titanium oxide.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] As electronic devices become lighter, thinner, and smaller, semiconductor packages are becoming smaller and thinner. The above-mentioned semiconductor packages are obtained by encapsulating semiconductor elements with a thermosetting resin encapsulant, and as the semiconductor packages become thinner, the encapsulation resin layer that encapsulates the semiconductor elements is also becoming thinner.

[0003] In resin-sealed semiconductor packages, various types of identification information such as manufacturing lot numbers and logos are printed on the surface of the sealing resin layer. Laser marking is known as one of the methods for printing on the surface of the sealing resin layer. Laser marking is a technology in which the surface of the sealing resin layer is scraped off and printed with a laser beam. With the laser marking method, the sealing resin layer is directly engraved, so additional processes such as cleaning are not required, and the production efficiency is higher than that of the printing method, and the durability of the printed part is improved.

[0004] Examples of encapsulating resin compositions that take into consideration laser marking properties include compositions disclosed in Patent Documents 1 to 3. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2006-278959 A [Patent Document 2] JP 2016-113566 A [Patent Document 3] JP 2018-162351 A Summary of the Invention [Problem to be solved by the invention]

[0006] By using a composition that can produce a cured product with a high dielectric constant, it is possible to miniaturize a semiconductor package. Therefore, in order to increase the dielectric constant of the cured product, a titanium-containing high dielectric filler may be added to the encapsulating resin composition. However, if the encapsulating resin composition contains a colorant such as carbon black together with the titanium-containing high dielectric filler, the encapsulating resin layer cannot be deeply scraped off by the laser light, and the laser processability may be insufficient.

[0007] One aspect of the present disclosure has been made in consideration of the above-mentioned conventional circumstances, and has an object to provide a molding resin composition that is excellent in laser processability and an electronic component device using the same. [Means for solving the problem]

[0008] Specific means for achieving the above object are as follows. <1> A hardening resin; an inorganic filler including a titanium-containing high dielectric filler; Carbon black, Black titanium oxide, A molding resin composition comprising: <2> The inorganic filler further contains at least one other inorganic filler selected from the group consisting of silica particles and alumina particles. <1> The molding resin composition according to claim 1. <3> The curable resin contains an epoxy resin, and the molding resin composition further contains a curing agent. <1> or <2> The molding resin composition according to claim 1. <4> The curing agent includes an active ester compound. <3> The molding resin composition according to claim 1. <5> The curing agent includes at least one other curing agent selected from the group consisting of a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent, and an active ester compound. <3> or <4> The molding resin composition according to claim 1. <6> The content of the titanium-containing high dielectric filler is 30% by volume to 80% by volume with respect to the total volume of the inorganic filler. <1> ~ <5> 10. The molding resin composition according to claim 9, <7> The total content of the carbon black and the black titanium oxide is 0.3% by mass to 4.0% by mass based on the entire molding resin composition. <1> ~ <6> 10. The molding resin composition according to claim 9, <8> Used in high frequency devices, <1> ~ <7> 10. The molding resin composition according to claim 9, <9> Used for antenna-in-package, <1> ~ <7> 10. The molding resin composition according to claim 9, <10> A support member; an electronic component disposed on the support member; The electronic components are sealed. <1> ~ <7> A cured product of the molding resin composition according to any one of the above items, An electronic component device comprising: <11> The electronic component includes an antenna. <10> The electronic component device according to claim 1 . Effect of the Invention

[0009] According to one aspect of the present disclosure, it is possible to provide a molding resin composition having excellent laser processability and an electronic component device using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the 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, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to the numerical values ​​and their ranges, and do not limit the present disclosure.

[0011] In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of corresponding substances. When multiple types of 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, the particles corresponding to each component may include 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. In the present disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire area when the area in which the layer or film is present is observed, as well as cases where the layer or film is formed over only a portion of the area.

[0012] <Molding resin composition> The molding resin composition of the present disclosure includes a curable resin, an inorganic filler including a titanium-containing high dielectric filler, carbon black, and black titanium oxide. The present inventors have found that even when an inorganic filler containing a titanium-containing high dielectric filler is used, the laser processability is improved by using carbon black and black titanium oxide in combination, and the laser can be dug deeper. Furthermore, the dielectric constant of the cured product of the molding resin composition can be adjusted by adjusting the content of the titanium-containing high dielectric filler. For example, by increasing the content of the titanium-containing high dielectric filler, it is possible to achieve both a high dielectric constant and a laser depth.

[0013] Hereinafter, each component constituting the encapsulating resin composition of the present disclosure will be described.

[0014] (curable resin) The molding resin composition in the present disclosure contains a curable resin. The curable resin may be either a thermosetting resin or a photocurable resin, and from the viewpoint of mass productivity, a thermosetting resin is preferable. Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, urethane resin, polyimide resin such as bismaleimide resin, polyamide resin, polyamideimide resin, silicone resin, acrylic resin, etc. From the viewpoint of moldability and electrical properties, the thermosetting resin is preferably at least one selected from the group consisting of epoxy resin and polyimide resin, more preferably at least one selected from the group consisting of epoxy resin and bismaleimide resin, and further preferably an epoxy resin. The molding resin composition may contain only one type of curable resin, or may contain two or more types of curable resin. Hereinafter, an epoxy resin will be described as an example of the curable resin.

[0015] -Epoxy resin- The molding resin composition preferably contains an epoxy resin as the curable resin. When the molding resin composition contains an epoxy resin as a curable resin, the content of the epoxy resin in 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. The content of the epoxy resin in the entire curable resin may be 100% by mass. The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.

[0016] Specific examples of epoxy resins include novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, 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., under an acidic catalyst; triphenylmethane-type epoxy resins obtained by epoxidizing a triphenylmethane-type phenolic resin obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc., under an acidic catalyst; and novolac-type epoxy resins obtained by co-condensing the above-mentioned phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst. Copolymerized epoxy resins obtained by epoxidizing resins; diphenylmethane-type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; 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, etc.; 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, etc. is replaced with a glycidyl group; dicyclopentadiene-type epoxy resins obtained by epoxidizing co-condensation resins of dicyclopentadiene and phenolic compounds;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 epoxy-modified epoxy resins in which the olefin bonds in the molecule have been epoxidized; 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 the epoxy resin 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; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Furthermore, epoxy-oxidized acrylic resins and the like can also be mentioned as epoxy resins. These epoxy resins may be used alone or in combination of two or more.;

[0017] The epoxy equivalent of the epoxy resin (molecular weight / number of epoxy groups) is not particularly limited. From the viewpoint of the 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 conforming to JIS K 7236:2009.

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

[0019] When the molding resin composition contains an epoxy resin as a curable resin, the mass proportion of the epoxy resin in the total amount of the molding 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, etc.

[0020] (hardening agent) When the curable resin includes an epoxy resin, the molding resin composition of the present disclosure preferably includes a curing agent.

[0021] The type of curing agent is not particularly limited, and can be selected from those generally used as curing agents for epoxy resins. The curing agent may be used alone or in combination of two or more. Examples of the curing agent 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, active ester compounds, etc. Among these, from the viewpoint of heat resistance, phenol-based curing agents or amine-based curing agents are preferred as the curing agent, and from the viewpoint of reduction in dielectric tangent, active ester compounds are preferred as the cured product. For example, the cured product may contain a phenol-based or amine-based curing agent and an active ester compound.

[0022] Examples of the phenol-based curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specific examples of the phenol-based curing agent include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; novolac-type phenol 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, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde, under an acid catalyst; and phenolic compounds synthesized from the above-mentioned phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like. Examples of the phenolic curing agent include aralkyl-type phenolic resins such as aryl aralkyl resins and naphthol aralkyl resins; paraxylylene-modified phenolic resins; 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 and dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acid catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used alone or in combination of two or more.

[0023] Specific examples of the amine-based curing agent include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane, aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, and 2-methylaniline, imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole, and imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline, etc. These amine-based curing agents may be used alone or in combination of two or more.

[0024] The content of the phenol resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and further preferably 15% by mass to 30% by mass, based on the total amount of the epoxy resin.

[0025] When the phenol curing agent contains a melamine-modified phenolic resin, the content of the melamine-modified phenolic resin is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and even more preferably 3% by mass to 10% by mass, based on the total amount of the epoxy resin. When the content of the melamine-modified phenolic resin is 1% by mass or more based on the total amount of the epoxy resin, the cured product of the molding resin composition tends to have improved adhesion (particularly adhesion at high temperatures) to adherends such as electronic components and support members on which the electronic components are mounted. When the content of the melamine-modified phenolic resin is 20% by mass or less based on the total amount of the epoxy resin, rapid gelation tends to be suppressed and fluidity can be ensured.

[0026] The reactive group equivalent of the phenol curing agent (e.g., hydroxyl group equivalent) or the active hydrogen equivalent of the amine curing agent is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance, and electrical reliability, it is preferably 10 g / eq to 1000 g / eq, and more preferably 30 g / eq to 500 g / eq. The hydroxyl equivalent in the case of a phenolic curing agent is a value calculated based on the hydroxyl value measured in accordance with JIS K0070: 1992. The active hydrogen equivalent in the case of an amine curing agent is a value calculated based on the amine value measured in accordance with JIS K7237: 1995.

[0027] When an active ester compound is used as a curing agent, the dielectric tangent of the cured product can be kept low compared to when a phenolic or amine curing agent is used as a curing agent. The reason for this is presumed to be as follows. In the reaction between an epoxy resin and a phenolic or amine curing agent, a secondary hydroxyl group is generated. In contrast, in the reaction between an epoxy resin and an active ester compound, an ester group is generated instead of a secondary hydroxyl group. Since an ester group has a lower polarity than a secondary hydroxyl group, a molding resin composition containing an active ester compound as a curing agent can reduce the dielectric tangent of the cured product compared to a molding resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent. In addition, while polar groups in the cured product increase the water absorption of the cured product, the polar group concentration of the cured product can be reduced by using an active ester compound as a curing agent, and the water absorption of the cured product can be reduced. By reducing the water absorption of the cured product, that is, by reducing the content of H2O, which is a polar molecule, the dielectric tangent of the cured product can be further reduced.

[0028] 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 active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esters of heterocyclic hydroxy compounds.

[0029] 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 having 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 having an aromatic compound as a polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring.

[0030] Specific examples of active ester compounds include aromatic esters obtained by condensation reaction between aromatic carboxylic acid and phenolic hydroxyl group. Among them, aromatic esters obtained by condensation reaction between aromatic carboxylic acid and phenolic hydroxyl group using a mixture of aromatic carboxylic acid components in which 2 to 4 hydrogen atoms of aromatic rings such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenylether, and diphenylsulfonic acid are substituted with carboxyl groups, monohydric phenols in which one hydrogen atom of the aromatic ring is substituted with hydroxyl groups, and polyhydric phenols in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with hydroxyl groups as raw materials are preferred. 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 preferred.

[0031] A specific example of the active ester compound is an active ester resin having a structure obtained by reacting a phenolic resin having a molecular structure in which a phenolic compound is bonded via an aliphatic cyclic hydrocarbon group with an aromatic dicarboxylic acid or its halide 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 preferable.

[0032] [ka]

[0033] In structural formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms; 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.

[0034] 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.

[0035] [ka]

[0036] [ka]

[0037] 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 JP2014-114352A.

[0038] [ka]

[0039] 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 a naphthoyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), and at least one of Z is an ester-forming structural moiety (z1).

[0040] 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 a naphthoyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), and at least one of Z is an ester-forming structural moiety (z1).

[0041] Specific examples of the compound represented by structural formula (2) include the following exemplary compounds (2-1) to (2-6).

[0042] [ka]

[0043] Specific examples of the compound represented by structural formula (3) include the following exemplary compounds (3-1) to (3-6).

[0044] [ka]

[0045] Commercially available products may be used as the active ester compound. Commercially available products of the active ester compound 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 active ester compounds containing an acetylated product of phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing a benzoylated product of phenol novolac.

[0046] The ester equivalent (molecular weight / number of ester groups) of the active ester compound is not particularly limited, and from the viewpoint of the 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.

[0047] The equivalent ratio of the epoxy resin to the curing agent (the number of moles of epoxy groups in the resin / the total number of moles of reactive groups, active hydrogen, and ester groups in the curing agent) is not particularly limited, and from the viewpoint of keeping the amount of each unreacted to a minimum, it is, for example, preferably 0.7 to 1.6, more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.2.

[0048] The softening point or melting point of the curing agent is not particularly limited. From the viewpoints of moldability and reflow resistance, the softening point or melting point of the curing agent is preferably 40° C. to 180° C., and from the viewpoint of handleability during production of the molding resin composition, it is more preferably 50° C. to 130° C. The melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0049] The curing agent preferably contains at least one other curing agent selected from the group consisting of phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents, and an active ester compound, and more preferably contains an active ester compound and a phenol-based curing agent. The mass ratio of the active ester compound to the total amount of the active ester compound and the phenol-based curing agent is preferably 40 mass% or more, more preferably 60 mass% or more, from the viewpoint of keeping the dielectric tangent of the cured product low. The mass ratio of the active ester compound to the total amount of the active ester compound and the phenol-based curing agent may be 80 mass% or less, or may be 70 mass% or less.

[0050] When the molding resin composition contains an epoxy resin and a curing agent, the content of curable resins other than the epoxy resin may be less than 5 mass%, may be 4 mass% or less, or may be 3 mass% or less, relative to the total amount of the molding resin composition.

[0051] (Cure accelerator) The molding resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited and can be selected depending on the type of epoxy resin, the desired properties of the molding resin composition, and the like.

[0052] Specifically, diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and Compounds with intramolecular polarization obtained by adding compounds with π bonds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, and diazophenylmethane to the compound; cyclic amidinium compounds such as tetraphenylborate salts, tetraphenylborate salts of DBN, tetraphenylborate salts of 2-ethyl-4-methylimidazole, and tetraphenylborate salts 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; primary phosphines such as ethylphosphine and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(diphenyl)phosphine, and the like; organic phosphines such as tertiary phosphines, such as 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 the complexes of the above organic phosphines or the above phosphine compounds and compounds having intramolecular polarization, such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, and other quinone compounds, and diazophenylmethane, and other compounds having a π bond;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-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, Examples of the compound include compounds having intramolecular polarization obtained by reacting a halogenated phenol compound such as bromo-2-naphthol or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation step; 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 and phenol compounds; phosphobetaine compounds; and adducts of phosphonium compounds and silane compounds. Examples of curing accelerators that allow low-temperature curing include an adduct of tributylphosphine and 1,4-benzoquinone, dimethylaminopyridine, 2-ethyl-4-methylimidazole, 2-methylimidazole, and 1-benzyl-2-methylimidazole. The curing accelerators may be used alone or in combination of two or more.

[0053] When the molding resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.1% by mass to 8% by mass based on the total amount of the epoxy resin and the curing agent.

[0054] (Inorganic filler) The molding resin composition contains an inorganic filler including a titanium-containing high dielectric filler.

[0055] The type of inorganic filler is not particularly limited as long as it contains a titanium-containing high dielectric filler, and may consist only of a titanium-containing high dielectric filler, or may consist of a titanium-containing high dielectric filler and other inorganic fillers.

[0056] The titanium-containing high dielectric filler is not particularly limited as long as it is a filler containing titanium element and has a high dielectric constant, and examples thereof include barium titanate, calcium titanate, strontium titanate, potassium titanate, magnesium titanate, lead titanate, aluminum titanate, lithium titanate, and zinc zirconate titanate. As the titanium-containing high dielectric filler, calcium titanate and strontium titanate are preferred, and calcium titanate is more preferred. The titanium-containing high dielectric filler may be used alone or in combination of two or more kinds. However, from the viewpoint of keeping the dielectric tangent of the cured product low, the content of barium titanate is preferably less than 1 volume %, more preferably less than 0.5 volume %, and even more preferably less than 0.1 volume %, based on the total inorganic filler.

[0057] Examples of other inorganic fillers include inorganic materials such as silica, such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having a flame retardant effect may be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. The other inorganic fillers preferably include at least one selected from the group consisting of silica particles and alumina particles. The other inorganic fillers may be used alone or in combination of two or more.

[0058] The inorganic filler may be in the form of powder, beads obtained by shaping the powder into spheroids, fibers, or the like.

[0059] The content of the titanium-containing high dielectric filler is preferably 5% by volume to 100% by volume, more preferably 10% by volume to 80% by volume, and even more preferably 30% by volume to 80% by volume, based on the total inorganic filler.

[0060] The content (vol %) of the titanium-containing high dielectric filler relative to the entire inorganic filler can be determined by the following method. A thin slice sample of the cured product of the molding resin composition is imaged with a scanning electron microscope (SEM). An arbitrary area S is identified in the SEM image, and the total area A of the inorganic filler contained in the area S is determined. Next, a SEM-EDX (energy dispersive X-ray spectrometer) is used to identify the elements of the inorganic filler, and the total area B of the titanium-containing high dielectric filler contained in the total area A of the inorganic filler is determined. The total area B of the titanium-containing high dielectric filler is divided by the total area A of the inorganic filler, and the value is converted to a percentage (%), and this value is the content (volume %) of the titanium-containing high dielectric filler relative to the entire inorganic filler. The area S is set to be sufficiently large relative to the size of the inorganic filler. For example, the area S is set to be large enough to contain 100 or more inorganic fillers. The area S may be the total area of ​​a plurality of cut surfaces.

[0061] The content of the inorganic filler is not particularly limited. From the viewpoint of fluidity and strength, the content of the inorganic filler is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 85% by volume, and even more preferably 40% by volume to 80% by volume, based on the entire molding resin composition. When the content of the inorganic filler is 30% by volume or more based on the entire molding resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less based on the entire molding resin composition, the increase in the viscosity of the molding resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better.

[0062] The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, an irregular shape, etc. The inorganic filler may be crushed. The titanium-containing high dielectric filler may be surface-treated.

[0063] The volume average particle size of the titanium-containing highly dielectric 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.

[0064] The average particle size of the other inorganic fillers is not particularly limited. For example, the volume average particle size is preferably 20 μm or less, more preferably 0.1 μm to 20 μm, even more preferably 0.2 μm to 18 μm, and particularly preferably 0.3 μm to 15 μm. When the volume average particle size is 20 μm or less, the filling ability into narrow gaps tends to be improved. Also, when the volume average particle size is 0.1 μm or more, the increase in viscosity of the molding resin composition tends to be further suppressed.

[0065] The volume average particle diameter of the inorganic filler can be measured as the volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.

[0066] (Carbon black and black titanium dioxide) The molding resin composition contains carbon black and black titanium oxide. The carbon black and the black titanium oxide may each independently be used alone or in combination of two or more kinds.

[0067] It is preferable that at least the black titanium oxide is surface-treated, and it is more preferable to use surface-treated black titanium oxide in combination with non-surface-treated carbon black.

[0068] Black titanium oxide is Ti n O (2n-1) (n is a positive integer). The black titanium dioxide Tin O (2n-1) It is preferable to use a black titanium oxide having n of 4 to 6. By making n 4 or more, the dispersibility of the black titanium oxide in the molding resin composition tends to be improved. On the other hand, by making n 6 or less, the printability by the laser marking method tends to be further improved. The molding resin composition contains black titanium oxides Ti4O7, Ti5O9, and Ti6O 11 It is preferable to include at least one of the following:

[0069] The surface-treated black titanium oxide includes black titanium oxide that has been surface-treated with a surface treatment agent. Examples of the surface treatment agent for black titanium oxide include coupling agents such as silane coupling agents, titanium coupling agents, etc. The coupling agents may be used alone or in combination of two or more.

[0070] Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0071] Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0072] Examples of methods for surface treating black titanium oxide include a method in which a solution containing a coupling agent is added to a slurry containing black titanium oxide, the mixture is stirred, and the surface-treated black titanium oxide is then separated by filtration or the like and dried, and a method in which a coupling agent is sprayed onto the black titanium oxide and then dried.

[0073] The average particle size of the black titanium oxide is not particularly limited. For example, the volume average particle size of the black titanium oxide is preferably 0.01 μm to 1 μm, more preferably 0.015 μm to 0.1 μm, and even more preferably 0.02 μm to 0.07 μm. When the volume average particle size of the black titanium oxide is 0.01 μm or more, the increase in viscosity of the molding resin composition tends to be more suppressed. When the volume average particle size of the black titanium oxide is 1 μm or less, the filling ability into narrow gaps tends to be more improved.

[0074] Examples of carbon black include acetylene black, ketjen black, thermal black, and furnace black.

[0075] The molding resin composition may contain colorants other than carbon black and black titanium oxide, such as known colorants including organic dyes, organic pigments, red lead, and red iron oxide.

[0076] From the viewpoint of improving printability by laser marking, the content of carbon black in the molding resin composition is preferably 0.1 to 1.0% by mass, and more preferably 0.2 to 0.8% by mass.

[0077] The content of black titanium oxide in the molding resin composition is preferably 0.2 to 3.0% by mass, and more preferably 0.5 to 2.0% by mass, from the viewpoint of improving printability by laser marking.

[0078] The total content of carbon black and black titanium oxide in the molding resin composition is preferably 0.3 to 4.0% by mass, and more preferably 0.5 to 3.0% by mass.

[0079] The content ratio of carbon black to black titanium oxide on a mass basis (carbon black / black titanium oxide) is preferably from 0.01 to 10.0, more preferably from 0.1 to 2.0, and even more preferably from 0.2 to 1.0.

[0080] (Various additives) In addition to the above-mentioned components, the molding resin composition may contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, stress relaxation agents, etc. The molding resin composition may contain various additives known in the art, as necessary, in addition to the additives exemplified below.

[0081] (Method for preparing molding resin composition) The method for preparing the molding resin composition is not particularly limited. When the molding resin composition is solid, a general method includes thoroughly mixing a predetermined amount of components with a mixer or the like, melt-kneading the components with a mixing roll, an extruder, or the like, cooling, and pulverizing the components. More specifically, for example, a method includes uniformly stirring and mixing a predetermined amount of the components described above, kneading the components with a kneader, roll, extruder, twin-screw extruder, or the like that has been heated to 70°C to 140°C in advance, cooling, and pulverizing the components. When the molding resin composition is in a liquid state, a typical method includes weighing out predetermined amounts of components and dispersing and kneading them using a three-roll mill, a crusher, a planetary mixer, a hard mixer, a homomixer, etc. In addition, a method using a master batch in which each component is pre-dispersed and pre-heated is preferred from the viewpoints of uniform dispersion and flowability.

[0082] When the molding resin composition is solid, the shape is not particularly limited, and examples thereof include powder, granules, tablets, pellets, etc. When the molding resin composition is in tablet or pellet form, the dimensions and mass are preferably set to be suitable for the molding conditions of the package from the viewpoint of handleability. When the molding resin composition is in a liquid state, the viscosity at 25° C. is preferably less than 1000 Pa·s, more preferably 800 Pa·s or less, and even more preferably 500 Pa·s or less. In this disclosure, the viscosity at 25° C. refers to a value measured at a shear rate of 10 revolutions per minute using a rotational shear viscometer equipped with a cone plate (diameter 48 mm, cone angle 1°).

[0083] (Uses of molding resin composition) The molding resin composition in this embodiment can be used, for example, in the manufacture of electronic component devices, particularly high-frequency devices, which will be described later. In particular, in recent years, with the spread of the fifth generation mobile communication system (5G), the semiconductor packages (PKGs) used in electronic device devices have become more sophisticated and smaller in size. As the PKGs become smaller and more sophisticated, the development of antenna-in-package (AiP, Antenna in Package), which is a PKG with an antenna function, is also underway. In AiP, the radio waves used for communication are becoming higher in frequency to accommodate the increase in the number of channels accompanying the diversification of information, and therefore, the sealing material is required to have both a high dielectric constant and a low dielectric loss tangent. As described above, the molding resin composition of the present embodiment can provide a cured product having both a high dielectric constant and a low dielectric loss tangent, and is therefore particularly suitable for use in antenna-in-package (AiP) applications in which an antenna disposed on a support member of a high-frequency device is encapsulated with the molding resin composition.

[0084] <Electronic component equipment> An electronic component device according to one embodiment of the present disclosure includes a support member, an electronic component disposed on the support member, and a cured product of the molding resin composition encapsulating the electronic component. Examples of electronic component devices include those (e.g., high-frequency devices) obtained by mounting electronic components (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, antennas, etc.) on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and sealing the resulting electronic component region with a molding resin composition.

[0085] The type of the support member is not particularly limited, and any support member that is 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 a wiring.

[0086] 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 sealed with the molding resin composition described above, may be sealed with another resin composition, or may not be sealed.

[0087] (Electronic component device manufacturing method) The method for manufacturing an electronic component device according to this embodiment includes the steps of placing an electronic component on a support member and encapsulating the electronic component with the molding 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. In addition, the types of the support member and electronic components used in the manufacture of the electronic component device are not particularly limited and support members and electronic components generally used in the manufacture of the electronic component device can be used.

[0088] Methods for encapsulating electronic parts using the molding resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is the most common. EXAMPLES

[0089] The above embodiment will be specifically described below using examples, but the scope of the above embodiment is not limited to these examples.

[0090] <Preparation of molding resin composition> Molding resin compositions of Examples and Comparative Examples were prepared by mixing the components shown below in the blending ratios (parts by mass) shown in Tables 1 and 2. This molding resin composition was solid at room temperature and normal pressure. In Tables 1 and 2, blank spaces indicate that the component is not included.

[0091] Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274g / eq Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 192g / eq

[0092] Hardener 1: Active ester compound, DIC Corporation, product name "EXB-8" Hardener 2: Melamine modified phenolic resin, reactive group equivalent 120g / eq Hardener 3: Biphenyl aralkyl type phenolic resin, hydroxyl equivalent 199g / eq

[0093] Curing accelerator: Triphenylphosphine / 1,4-benzoquinone adduct Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane Release agent: Montan acid ester wax

[0094] Carbon black 1: Carbon black, Mitsubishi Chemical Corporation, product name "MA100" Carbon black 2: Carbon black, Mitsubishi Chemical Corporation, product name "MA600" Carbon black 3: Carbon black, Tokai Carbon Co., Ltd., product name "#40FF" Carbon black 4: Carbon black, Tokai Carbon Co., Ltd., product name "#20FF"

[0095] Carbodiimide: Cyclic carbodiimide Silicone: Silicone resin

[0096] Inorganic filler 1: Alumina particles, volume average particle size: 13 μm, specific surface area: approx. 1.0 m 2 / g Inorganic filler 2: Alumina particles, volume average particle size: 1.5 μm, specific surface area: approx. 1.0 m 2 / g Inorganic filler 3: Alumina particles, volume average particle size: 0.3 μm, specific surface area: approx. 6.0 m 2 / g Inorganic filler 4: Calcium titanate particles, volume average particle size: 0.25 μm, specific surface area: approx. 14.0 m 2 / g Inorganic filler 5: Calcium titanate particles, volume average particle size: 23 μm, specific surface area: approx. 1.0 m 2 / g Black titanium oxide: Black titanium oxide particles surface-treated with a coupling agent, volume average particle size: 0.6 μm, specific surface area: approx. 40 m 2 / g

[0097] The volume average particle size of each of the inorganic fillers is a value obtained by the following measurement. Specifically, first, the inorganic filler was added to a dispersion medium (water) in a range of 0.01% by mass to 0.1% by mass, and dispersed for 5 minutes in a bath-type ultrasonic cleaner. 5 ml of the obtained dispersion was poured into a cell, and the particle size distribution was measured at 25° C. using a laser diffraction / scattering type particle size distribution measuring device (HORIBA, Ltd., LA920). The particle size at an integrated value of 50% (volume basis) in the obtained particle size distribution was defined as the volume average particle size.

[0098] <Evaluation of molding resin composition> (Dielectric constant and dielectric tangent) The molding resin composition was charged into a vacuum hand press and molded under the conditions of a mold temperature of 175°C, molding pressure of 6.9MPa, and curing time of 600 seconds. Post-curing was performed at 175°C for 6 hours to obtain a plate-shaped cured product (length 12.5mm, width 25mm, thickness 0.2mm). The plate-shaped cured product was used as a test piece and the relative dielectric constant and dielectric loss tangent were measured at 25±3°C and 10GHz using a dielectric constant measuring device (Agilent Technologies, product name "Network Analyzer N5227A"). The results are shown in Tables 1 and 2 ("Relative Dielectric Constant" and "Dielectric Loss Tangent" in the tables).

[0099] (Fluidity: Spiral flow) Using a spiral flow measurement mold conforming to EMMI-1-66, the molding resin composition was molded under the conditions of a mold temperature of 175°C, molding pressure of 6.9 MPa, and curing time of 90 seconds, and the flow distance (cm) was measured. The results are shown in Tables 1 and 2 ("Flow distance (cm)" in the tables).

[0100] (Printing evaluation) Characters were marked on the cured product of the molding resin composition using a YAG laser marker (MD-H9800) manufactured by Keyence Corporation under the conditions of 50% output of the excitation source, a Q-switch frequency of 10 kHz, and a scan speed of 500 mm / sec. The marking depth (μm) at which the marked characters were visible was determined using a digital microscope (VHX-7000) manufactured by Keyence Corporation. The results are shown in Tables 1 and 2.

[0101] [Table 1]

[0102] [Table 2]

[0103] As shown in Tables 1 and 2, it is apparent that the molding resin compositions of the Examples have better print evaluation than the molding resin compositions of the Comparative Examples.

Claims

1. A hardening resin; an inorganic filler including a titanium-containing high dielectric filler; Carbon black, Black titanium oxide, A molding resin composition comprising:

2. 2. The molding resin composition according to claim 1, wherein the inorganic filler further contains another inorganic filler which is at least one kind selected from the group consisting of silica particles and alumina particles.

3. 2. The molding resin composition of claim 1, wherein the curable resin comprises an epoxy resin, and the molding resin composition further comprises a curing agent.

4. The molding resin composition according to claim 3 , wherein the curing agent comprises an active ester compound.

5. 4. The molding resin composition according to claim 3, wherein the curing agent comprises at least one other curing agent selected from the group consisting of a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent, and an active ester compound.

6. 2. The molding resin composition according to claim 1, wherein the content of said titanium-containing high dielectric filler is 30% by volume to 80% by volume based on the total volume of said inorganic filler.

7. 2. The molding resin composition according to claim 1, wherein the total content of the carbon black and the black titanium oxide is 0.3% by mass to 4.0% by mass based on the entire molding resin composition.

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

9. The molding resin composition according to any one of claims 1 to 7, which is used for an antenna-in-package.

10. A support member; an electronic component disposed on the support member; A cured product of the molding resin composition according to any one of claims 1 to 7 which encapsulates the electronic component; An electronic component device comprising:

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

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