Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device

Abstract

To provide a resin composition for sealing that can suitably fill a narrow passage and can give a cured article having a low dielectric loss tangent, an electronic component device sealed therewith, and a method for manufacturing an electronic component device sealed therewith.SOLUTION: The present invention provides a resin composition for sealing for use in narrow passage filling, the composition containing an epoxy resin, a hardening agent and an inorganic filler material. The hardening agent contains an active ester compound, and the average particle diameter of the inorganic filler material is less than 10 μm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an encapsulating resin composition, an electronic component device, and a method for manufacturing an electronic component device. [Background technology]

[0002] The amount of transmission loss that occurs when radio waves transmitted for communication are converted into heat in a dielectric is expressed as the product of frequency, the square root of the relative dielectric constant, and the dielectric loss tangent. In other words, since the transmission signal is more likely to be converted into heat in proportion to the frequency, the higher the frequency band, the lower the dielectric properties required for communication component materials in order to suppress transmission loss.

[0003] For example, Patent Documents 1 and 2 disclose thermosetting resin compositions containing an active ester resin as a curing agent for epoxy resins, which are said to be capable of keeping the dielectric loss tangent of the cured product low. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-246367 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-114352 Summary of the Invention [Problem to be solved by the invention]

[0005] In the field of information and communications, radio waves are becoming increasingly higher in frequency as the number of channels and the amount of information transmitted increase. Currently, studies on fifth-generation mobile communications systems are underway worldwide, with several candidate frequency bands in the range of approximately 30 GHz to 70 GHz being identified. As wireless communications will become mainstream in the future at such high frequencies, materials for communications components are being required to have even lower dielectric loss tangents.

[0006] In addition, as semiconductor devices become smaller, thinner, and more functional, bump pitches or spacing between elements become narrower, and therefore, there is a demand for encapsulating resin compositions that are excellent in narrow-path filling properties.

[0007] The embodiments of the present disclosure have been made under the above circumstances.

[0008] An object of the present disclosure is to provide an encapsulating resin composition that has excellent narrow-path filling properties and a low dielectric tangent of the cured product, an electronic component device encapsulated with the same, and a method for manufacturing an electronic component device encapsulated with the same. [Means for solving the problem]

[0009] Specific means for solving the above problems include the following aspects.

[0010] [1] An encapsulating resin composition for use in filling narrow passages, comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent contains an active ester compound, and the inorganic filler has an average particle size of less than 10 μm. [2] The encapsulating resin composition according to [1], wherein the inorganic filler has a maximum particle size of less than 20 μm. [3] The encapsulating resin composition according to [1] or [2], which is for mold underfill. [4] An electronic component device comprising: a support member, an element placed on the support member, and a cured product of the encapsulating resin composition according to any one of [1] to [3], which fills a narrow path around the element. [5] A method for manufacturing an electronic component device, comprising the steps of: placing an element on a support member; and filling a narrow passage around the element with the encapsulating resin composition according to any one of [1] to [3]. [Effects of the Invention]

[0011] According to the present disclosure, there are provided an encapsulating resin composition that has excellent narrow path filling properties and a low dielectric tangent of the cured product, an electronic component device encapsulated with the same, and a method for manufacturing an electronic component device encapsulated with the same. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 2 is a top view (partially perspective view) illustrating a test chip used in the examples. [Figure 2] FIG. 2 is a cross-sectional view illustrating a test chip used in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the composition may contain multiple types of particles corresponding to each component. 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. When embodiments of the present disclosure are described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each drawing are conceptual, and the relative size relationships between the components are not limited to these.

[0014] <Sealing resin composition> The encapsulating resin composition of the present disclosure is an encapsulating resin composition for filling narrow passages, which contains an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent contains an active ester compound, and the inorganic filler has an average particle size of less than 10 μm.

[0015] The narrow passage in which the encapsulating resin composition of the present disclosure is used refers to a gap having at least one of a height and a width of 100 μm or less. Examples of the narrow passage include a gap between a support member and an element, a gap between adjacent elements, and the like.

[0016] The encapsulating resin composition of the present disclosure may be used to fill narrow passages in electronic component devices, and may also be used to seal a portion of a space other than the narrow passages in an electronic component device, or the entire electronic component device. Examples of the above-mentioned embodiment include an encapsulating resin composition for mold underfill (MUF) that encapsulates an element placed on a support member and fills the gap between the support member and the element; an encapsulating resin composition for SiP (system in a package); and the like.

[0017] In the present disclosure, an active ester compound refers to a compound that has one or more ester groups in one molecule that react with an epoxy group and has the ability to harden an epoxy resin.

[0018] Conventionally, phenolic curing agents, amine curing agents, etc. have generally been used as curing agents for epoxy resins, but secondary hydroxyl groups are generated in the reaction between an epoxy resin and a phenolic curing agent or an amine curing agent. In contrast, ester groups are generated instead of secondary hydroxyl groups in the reaction between an epoxy resin and an activated ester compound. Because ester groups have lower polarity than secondary hydroxyl groups, the encapsulating resin composition of the present disclosure can reduce the dielectric tangent of the cured product compared to encapsulating resin compositions containing only a curing agent that generates secondary hydroxyl groups as a curing agent.

[0019] The encapsulating resin composition of the present disclosure has an inorganic filler with an average particle size of less than 10 μm, and therefore has excellent narrow-path filling properties. This is presumably because the inorganic filler is less likely to clog narrow paths when a melt of the encapsulating resin composition flows through the narrow paths. In the encapsulating resin composition of the present disclosure, the lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 3 μm or more, for example, from the viewpoint of suppressing aggregation of the inorganic filler particles.

[0020] (epoxy resin) The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.

[0021] Specific examples of epoxy resins include novolac epoxy resins (phenol novolac epoxy resins, orthocresol novolac epoxy resins, etc.) obtained by epoxidizing novolac resins obtained by condensing or co-condensing, under an acidic catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc.; triphenylmethane epoxy resins obtained by epoxidizing triphenylmethane phenolic resins obtained by condensing or co-condensing, under an acidic catalyst, the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc.; and novolac resins obtained by co-condensing, under an acidic catalyst, the above-mentioned phenolic compound and naphthol compound with an aldehyde compound. diphenylmethane-type epoxy resins, which are diglycidyl ethers of bisphenol A, bisphenol F, 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 the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; and dicyclopentadiene-type epoxy resins, which are epoxidized 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 produced by epoxidizing the olefin bonds in the molecule; 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; dicyclopentadiene-modified epoxy resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins; and cyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include cyclopentadiene-modified epoxy resins, which are glycidyl ethers of fatty acids; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins, such as phenol aralkyl resins and naphthol aralkyl resins. Further examples of suitable epoxy resins include epoxidized acrylic resins. These epoxy resins may be used alone or in combination of two or more.

[0022] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited, but from the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

[0023] The epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.

[0024] When the epoxy resin is solid, its softening point or melting point is not particularly limited, but is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of handleability during preparation of the encapsulating resin composition.

[0025] 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).

[0026] The content of the epoxy resin in the encapsulating resin composition is preferably 0.5 to 50% by mass, more preferably 2 to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, etc.

[0027] (hardening agent) The encapsulating resin composition of the present disclosure includes at least an active ester compound as a curing agent. The encapsulating resin composition of the present disclosure may include a curing agent other than the active ester compound.

[0028] As described above, the encapsulating resin composition of the present disclosure can reduce the dielectric loss tangent of the cured product by using an active ester compound as a curing agent. Furthermore, polar groups in the cured product increase the cured product's water absorption, and using an active ester compound as a curing agent can reduce the polar group concentration of the cured product, thereby suppressing the cured product's water absorption. Furthermore, by suppressing the cured product's water absorption, i.e., by suppressing the content of HO, a polar molecule, the dielectric tangent of the cured product can be further reduced. The cured product's water absorption is preferably 0% to 0.35%, more preferably 0% to 0.30%, and even more preferably 0% to 0.25%. The water absorption of the cured product is the mass gain determined by a pressure cooker test (121°C, 2.1 atmospheres, 24 hours).

[0029] The type of active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with an epoxy group.

[0030] Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an ester of a heterocyclic hydroxy compound.

[0031] Examples of active ester compounds include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds using an aliphatic compound as a polycondensation component tend to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain. Ester compounds using an aromatic compound as a polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring.

[0032] Specific examples of activated ester compounds include aromatic esters obtained by the condensation reaction of an aromatic carboxylic acid with a phenolic hydroxyl group. Among these, aromatic esters obtained by the condensation reaction of an aromatic carboxylic acid with a phenolic hydroxyl group using a mixture of raw materials: an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms on the aromatic ring of benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenylether, diphenylsulfonic acid, etc. are substituted with carboxyl groups; a monohydric phenol in which one hydrogen atom on the aromatic ring is substituted with a hydroxyl group; and a polyhydric phenol in which 2 to 4 hydrogen atoms on the aromatic ring are substituted with a hydroxyl group. That is, aromatic esters having structural units derived from the aromatic carboxylic acid component, structural units derived from the monohydric phenol, and structural units derived from the polyhydric phenol are preferred.

[0033] Specific examples of the active ester compound include an active ester resin having a structure obtained by reacting a phenolic resin having a molecular structure in which phenolic compounds are linked via alicyclic hydrocarbon groups 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 preferred.

[0034] [ka]

[0035] In structural formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms; X represents a benzene ring, a 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.

[0036] 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.

[0037] [ka]

[0038] [ka]

[0039] Other specific examples of the active ester compound include a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3), which are described in JP 2014-114352 A.

[0040] [ka]

[0041] In structural formula (2), R 1 and R 2are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Z is an ester-forming structural moiety (z1) selected from the group consisting of a benzoyl group, a 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).

[0042] 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 a benzoyl group, a 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).

[0043] Specific examples of the compound represented by structural formula (2) include the following exemplary compounds (2-1) to (2-6).

[0044] [ka]

[0045] Specific examples of the compound represented by structural formula (3) include the following exemplary compounds (3-1) to (3-6).

[0046] [ka]

[0047] Commercially available active ester compounds may be used. Examples of commercially available active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451," "EXB9460," "EXB9460S," and "HPC-8000-65T" (manufactured by DIC Corporation); active ester compounds containing an aromatic structure such as "EXB9416-70BK," "EXB-8," and "EXB-9425" (manufactured by DIC Corporation); active ester compounds containing an acetylated phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation); and active ester compounds containing a benzoylated phenol novolac such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

[0048] The active ester compounds may be used alone or in combination of two or more.

[0049] The ester group equivalent of the active ester compound is not particularly limited, but from the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 150 g / eq to 400 g / eq, more preferably 170 g / eq to 300 g / eq, and even more preferably 200 g / eq to 250 g / eq.

[0050] The ester group equivalent of the active ester compound is a value measured by a method in accordance with JIS K 0070:1992.

[0051] The equivalent ratio of the epoxy resin to the active ester compound (ester group / epoxy group) is preferably 0.9 or more, more preferably 0.95 or more, and even more preferably 0.97 or more, from the viewpoint of keeping the dielectric loss tangent of the cured product low. The equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, and even more preferably 1.03 or less, from the viewpoint of minimizing the amount of unreacted active ester compound.

[0052] The curing agent may contain other curing agents in addition to the active ester compound. In this case, the type of other curing agent is not particularly limited and can be selected depending on the desired properties of the encapsulating resin composition. Examples of other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents.

[0053] Specific examples of phenolic curing agents include polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolak-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde, under an acidic catalyst; and resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or the like. Examples of suitable phenol curing agents include aralkyl-type phenolic resins such as phenol 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 with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerization of two or more of these. These phenolic curing agents may be used alone or in combination of two or more.

[0054] The functional group equivalent of other curing agents (hydroxyl group equivalent in the case of phenolic curing agents) is not particularly limited, but from the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0055] The functional group equivalent weight of other curing agents (hydroxyl group equivalent weight in the case of phenolic curing agents) is specified in JIS K The value is measured by a method conforming to 0070:1992.

[0056] When the curing agent is solid, its softening point or melting point is not particularly limited, but is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of handleability during production of the encapsulating resin composition.

[0057] 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.

[0058] Equivalent ratio of epoxy resin to all hardeners (active ester compounds and other hardeners) That is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent / number of functional groups in the epoxy resin) is not particularly limited. From the viewpoint of minimizing the amount of unreacted components, it is preferably set in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is even more preferably set in the range of 0.8 to 1.2.

[0059] The content of the active ester compound relative to the total mass of the active ester compound and other curing agents is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of keeping the dielectric loss tangent of the cured product low.

[0060] The total content of the epoxy resin and the active ester compound relative to the total mass of the epoxy resin, the active ester compound, and other curing agents is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more, from the viewpoint of keeping the dielectric loss tangent of the cured product low.

[0061] (curing accelerator) The encapsulating 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 or curing agent, the desired properties of the encapsulating resin composition, and the like.

[0062] Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or their derivatives; 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 to these compounds; diazophenylmethane; and tetraphenyl benzoquinone. cyclic amidinium compounds and isocyanate adducts such as tetraphenylborate salts of DBN, tetraphenylborate salts of 2-ethyl-4-methylimidazole, and tetraphenylborate salts of N-methylmorpholine; isocyanate adducts of DBU, isocyanate adducts of DBN, isocyanate adducts of 2-ethyl-4-methylimidazole, and isocyanate adducts 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;tertiary phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine; phosphine compounds such as complexes of the above tertiary phosphines with organoborons; complexes of the above tertiary phosphines or the above phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, and 2,6-dimethylbenzoquinone; compounds having intramolecular polarization obtained by adding a compound having a π bond, such as quinone compounds such as 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, and diazophenylmethane; compounds having intramolecular polarization obtained by adding a compound having a π bond, such as the above-mentioned tertiary phosphines or the above-mentioned phosphine compounds, and 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; Examples of compounds having intramolecular polarization include compounds obtained by reacting a halogenated phenol compound such as 1-methylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation step; tetra-substituted phosphonium compounds such as tetraphenylphosphonium, and tetra-substituted phosphonium and tetra-substituted borates that do not have a phenyl group bonded to the boron atom, such as tetra-p-tolylborate; salts of tetraphenylphosphonium and phenol compounds; and salts of tetraalkylphosphonium and partial hydrolysates of aromatic carboxylic acid anhydrides.

[0063] When the encapsulating resin composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). When the amount of the curing accelerator is 0.1 part by mass or more per 100 parts by mass of the resin component, the composition tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin component, the curing speed is not too fast, and a good molded product tends to be obtained.

[0064] (Inorganic filler) The encapsulating resin composition of the present disclosure contains an inorganic filler having an average particle size of less than 10 μm. From the viewpoint of improving narrow passage filling ability, the average particle size of the inorganic filler is less than 10 μm, and preferably less than 9 μm. From the viewpoint of suppressing aggregation of the inorganic filler particles, the average particle size of the inorganic filler is preferably 3 μm or more, and more preferably 5 μm or more.

[0065] In the encapsulating resin composition of the present disclosure, from the viewpoint of further improving the narrow passage filling ability, the maximum particle size of the inorganic filler contained therein is preferably less than 30 μm, more preferably less than 25 μm, and even more preferably less than 20 μm.

[0066] The average particle size of the inorganic filler is the arithmetic mean of the major axes of 100 randomly selected inorganic fillers in an image of a thin sample of the encapsulating resin composition or its cured product taken with a scanning electron microscope. The maximum particle size of the inorganic filler is the largest of the major axes of the 100 randomly selected inorganic fillers.

[0067] The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay, and mica. Inorganic fillers with flame retardant properties may also be used. Examples of inorganic fillers with flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

[0068] Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. The inorganic filler may be in the form of powder, beads obtained by sphericizing powder, fiber, etc.

[0069] The content of the inorganic filler contained in the encapsulating resin composition is not particularly limited. From the viewpoint of fluidity and strength, the content is preferably 30 to 90% by volume of the entire encapsulating resin composition, more preferably 35 to 80% by volume, and even more preferably 40 to 70% by volume. When the content of the inorganic filler is 30% by volume or more of the entire encapsulating resin composition, the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire encapsulating resin composition, an increase in the viscosity of the encapsulating resin composition is suppressed, and the fluidity is further improved, tending to improve moldability.

[0070] [Various additives] In addition to the above-mentioned components, the encapsulating resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, etc. The encapsulating resin composition may contain various additives known in the art, as needed, in addition to the additives exemplified below.

[0071] (coupling agent) The encapsulating resin composition may contain a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the encapsulating resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate compounds, and aluminum / zirconium-based compounds.

[0072] When the encapsulating 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, per 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, adhesion to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, moldability of the package tends to be further improved.

[0073] (Ion exchanger) The resin composition for sealing may contain an ion exchanger. From the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed, it is preferable that the resin composition for sealing contains an ion exchanger. The ion exchanger is not particularly limited, and a conventionally known one can be used. Specifically, examples thereof include hydrotalcite compounds and metal hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0074] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≦ 0.5, m is a positive number)

[0075] When the resin composition for sealing contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

[0076] (Release agent) The resin composition for sealing may contain a release agent from the viewpoint of obtaining good releasability from a mold during molding. The release agent is not particularly limited, and a conventionally known one can be used. Specifically examples thereof include higher fatty acids such as carnauba wax, montanic acid, and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.

[0077] When the encapsulating resin composition contains a release agent, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). When the amount of the release agent is 0.01 part by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When the amount is 10 parts by mass or less, better adhesion tends to be obtained.

[0078] (Flame retardant) The encapsulating resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0079] When the encapsulating resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect. For example, the amount is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

[0080] (coloring agent) The encapsulating resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. The colorant may be used alone or in combination of two or more.

[0081] (Method for preparing encapsulating resin composition) The method for preparing the encapsulating resin composition is not particularly limited. A typical method includes thoroughly mixing predetermined amounts of components using a mixer or the like, melt-kneading the mixture using a mixing roll, extruder, or the like, cooling, and pulverizing the mixture. More specifically, a method includes uniformly stirring and mixing predetermined amounts of the components described above, kneading the mixture using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, cooling, and pulverizing the mixture.

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

[0083] <Electronic component equipment> An electronic component device according to one embodiment of the present disclosure includes a support member, an element disposed on the support member, and a cured product of the encapsulating resin composition according to the present disclosure that fills a narrow passage around the element.

[0084] An electronic component device according to an embodiment of the present disclosure has a narrow passage filled with the encapsulating resin composition according to the present disclosure. Examples of the narrow passage include a gap between a support member and an element, a gap between adjacent elements, and the like. The electronic component device according to an embodiment of the present disclosure has a narrow passage filled with the encapsulating resin composition according to the present disclosure. The body may be encapsulated with the encapsulating resin composition of the present disclosure.

[0085] Examples of electronic component devices include devices obtained by mounting elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) 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 then encapsulating the resulting element portion with an encapsulating resin composition. More specifically, a DIP (Dual Inline Package) is a package that has a structure in which an element is fixed on a lead frame, and terminal portions of the element, such as bonding pads, are connected to lead portions by wire bonding, bumps, or the like, and then sealed by transfer molding or the like using a sealing resin composition. General resin-sealed ICs such as PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which elements connected to a tape carrier by bumps are sealed with an encapsulating resin composition; COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc. having a structure in which elements connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, etc. are sealed with an encapsulating resin composition; BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Array) having a structure in which elements are mounted on the surface of a support member having terminals for wiring board connection formed on the back side, and the elements are connected to the wiring formed on the support member by bumps or wire bonding, and then the elements are sealed with an encapsulating resin composition. Package); Examples include SiP (system in a package), which encapsulates multiple elements in a single package.

[0086] <Electronic component device manufacturing method> The method for manufacturing an electronic component device of the present disclosure includes the steps of placing an element on a support member and filling a narrow passage around the element with the encapsulating resin composition of the present disclosure.

[0087] 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 support members and elements used in the manufacture of electronic component devices are not particularly limited and support members and elements commonly used in the manufacture of electronic component devices can be used.

[0088] The step of filling the narrow passage around the element with the encapsulating resin composition of the present disclosure may be a step of sealing a part of the space other than the narrow passage in the electronic component device or the entire electronic component device at the same time as filling the narrow passage around the element.

[0089] Methods for filling narrow passages around elements using the encapsulating resin composition of the present disclosure include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is the most common. [Example]

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

[0091] <Preparation of encapsulating resin composition> The encapsulating resin compositions of Examples and Comparative Examples were prepared by mixing the components shown below in the blending ratios shown in Table 1. The encapsulating resin compositions were solid at room temperature and normal pressure.

[0092] Epoxy resin 1: Biphenyl aralkyl epoxy resin, epoxy equivalent 274g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000") Epoxy resin 2: Triphenylmethane type epoxy resin, epoxy equivalent weight 167g / eq (Mitsubishi Chemical Corporation, product name "1032H60") Epoxy resin 3: Biphenyl type epoxy resin, epoxy equivalent weight 192g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

[0093] Active ester compound 1: DIC Corporation, product name "EXB-8" Active ester compound 2: DIC Corporation, product name "EXB-9425" Phenol curing agent 1: Phenol aralkyl resin, hydroxyl equivalent 175g / eq (Meiwa Kasei Co., Ltd., product name "MEH7800SS")

[0094] Curing accelerator 1: Triphenylphosphine / 1,4-benzoquinone adduct Curing accelerator 2: Imidazole compound (Shikoku Chemicals Corporation, product name "Curesol 2E4MZ")

[0095] Filler 1: Fused silica (DENKA, product name "FB-310MDC") Filler 2: Fused silica (Micron, product name "ST7010-2") Filler 3: Fused silica (Admatechs, product name "SO-25R") Filler 4: Fused silica (DENKA, product name "FB-9454FC") Filler 5: Fused silica (Micron, product name "ST7010-3")

[0096] Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573") Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-803") Release agent: Montan acid ester wax (Clariant Japan Co., Ltd., product name "HW-E") Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")

[0097] <Performance evaluation of encapsulating resin composition> (Average particle size and maximum particle size of inorganic filler) In an image of a thin sample of the encapsulating resin composition taken with a scanning electron microscope, the major axis (μm) of 100 randomly selected inorganic fillers was measured, and the arithmetic average was taken as the average particle size. The maximum value of the major axis (μm) of the 100 particles was taken as the maximum particle size.

[0098] (Spiral Flow) Using a spiral flow measurement mold conforming to EMMI-1-66, the encapsulating resin composition was molded under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance (cm) was determined.

[0099] (Narrow passage filling property) A test chip was prepared in the form shown in Figures 1 and 2. Three dies 3 (10 mm long x 10 mm wide x 250 μm thick) obtained by dicing a silicon wafer were placed on a substrate 1 (50 mm long x 250 mm wide x 0.2 mm thick) via die attach tape 6 (1.0 mm wide x 40 μm thick), and pressure-bonded at 200°C for 10 seconds. Next, the encapsulating resin composition was charged into a transfer molding machine and molded under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 150 seconds, followed by post-curing for 5 hours at 180°C. The molding dimensions were 50 mm length x 250 mm width x 0.5 mm thickness on substrate 1. A 1 mm gap visible between the die 3 and the substrate 1 from the surface opposite to the element mounting surface 2 The areas of the above voids were measured to determine the total area.

[0100] (relative permittivity and dielectric loss tangent) The encapsulating resin composition was loaded into a vacuum hand press and molded under conditions of a mold temperature of 175°C, molding pressure of 6.9 MPa, and curing time of 600 seconds. Post-curing was performed at 180°C for 6 hours to obtain a plate-shaped cured product (12.5 mm long, 25 mm wide, 0.2 mm thick). This plate-shaped cured product was used as a test specimen and its relative permittivity and dielectric loss tangent were measured at a temperature of 25±3°C and approximately 60 GHz using a dielectric constant measurement device (Agilent Technologies, product name "Network Analyzer N5227A").

[0101] (Water absorption rate) Immediately after production, the plate-shaped cured product was placed in a pressure cooker testing device at 121°C / 2.1 atmospheres, removed after 24 hours, and the increase in mass (%) from the mass immediately before placement was determined.

[0102] [Table 1]

[0103] All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. [Explanation of symbols]

[0104] 1: Circuit board 3: Die 6: Die attach tape

Claims

1. Contains an epoxy resin, a curing agent, and an inorganic filler, The curing agent contains an active ester compound containing a compound represented by the following structural formula (1): 【Chemistry 1】 [In structural formula (1), R 1 is an alkyl group having 1 to 4 carbon atoms; X is a benzene ring, a 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 is the average number of repetitions and is 0.25 to 1.5.] The average particle size of the inorganic filler is less than 10 μm. For use in narrow passage filling, An encapsulating resin composition in the form of a powder, granules, or tablet, which is solid at 25°C and atmospheric pressure, The encapsulating resin composition has a flow distance of 142 cm to 180 cm when molded using a spiral flow measurement mold conforming to EMMI-1-66 under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds.

2. The encapsulating resin composition according to claim 1 , wherein the inorganic filler has a maximum particle size of less than 20 μm.

3. 3. The encapsulating resin composition according to claim 1, wherein the epoxy resin comprises a biphenyl-type epoxy resin different from a phenol aralkyl-type epoxy resin having a biphenyl skeleton.

4. 4. The encapsulating resin composition according to claim 1, wherein a content of the active ester compound relative to a total amount of the curing agent is 80 mass% or more, and an average particle size of the inorganic filler is 3 μm or more.

5. The encapsulating resin composition according to any one of claims 1 to 4, further comprising at least one curing accelerator selected from the group consisting of an adduct of a tertiary phosphine and a quinone compound and 2-ethyl-4-methylimidazole.

6. The encapsulating resin composition according to any one of claims 1 to 5, which is for use in low-pressure transfer molding, injection molding, or compression molding.

7. The encapsulating resin composition according to any one of claims 1 to 5, which is used for mold underfill.

8. A support member; an element disposed on the support member; a cured product of the encapsulating resin composition according to any one of claims 1 to 7, which fills a narrow path around the element; and An electronic component device comprising:

9. placing the device on a support member; a step of filling a narrow path around the element with the encapsulating resin composition according to any one of claims 1 to 7; A method for manufacturing an electronic component device, comprising:

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