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

Abstract

The present invention provides a encapsulating resin composition with a low dielectric loss tangent of the cured product, an electronic component device encapsulated using the same, and a method for manufacturing an electronic component device encapsulated using the same. [Solution] A encapsulating resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent contains an active ester compound, and the average particle size of the inorganic filler is 5 μm to 100 μm.

Description

Technical Field

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

Background Art

[0002] The amount of transmission loss generated by the heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the frequency, the square root of the relative permittivity, and the dielectric tangent. That is, since the transmission signal is more likely to change into heat in proportion to the frequency, lower dielectric characteristics are required for the material of the communication member in the higher frequency band in order to suppress transmission loss.

[0003] For example, Patent Documents 1 and 2 disclose a thermosetting resin composition containing an active ester resin as a curing agent for an epoxy resin, and it is said that the dielectric tangent of the cured product can be kept low.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the field of information communication, with the increase in the number of channels and the amount of information transmitted, the high-frequencyization of radio waves is progressing. Currently, the study of the fifth-generation mobile communication system is being advanced worldwide, and some candidates for the frequency band to be used are in the range of about 30 GHz to 70 GHz. In the future, since the mainstream of wireless communication will be communication in such a high-frequency band, further reduction of the dielectric tangent is required for the material of the communication member.

[0006] Embodiments of the present disclosure have been made under the above circumstances.

[0007] The object of this disclosure is to provide a encapsulating resin composition with a low dielectric loss tangent of the cured product, an electronic component device encapsulated using the same, and a method for manufacturing an electronic component device encapsulated using the same. [Means for solving the problem]

[0008] The following embodiments are included as specific means for solving the aforementioned problems.

[0009] [1] A encapsulating resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent contains an active ester compound, and the average particle size of the inorganic filler is 5 μm to 100 μm. [2] An electronic component device comprising a support member, an element disposed on the support member, and a cured product of the sealing resin composition described in [1] that seals the element. [3] A method for manufacturing an electronic component device, comprising the steps of arranging an element on a support member and sealing the element with the sealing resin composition described in [1]. [Effects of the Invention]

[0010] According to this disclosure, a encapsulating resin composition with a low dielectric loss tangent of the cured product, an electronic component device encapsulated using the same, and a method for manufacturing an electronic component device encapsulated using the same are provided. [Modes for carrying out the invention]

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

[0012] <Sealing resin composition> The sealing resin composition of this disclosure contains an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent contains an active ester compound, and the average particle size of the inorganic filler is 5 μm to 100 μm.

[0013] In this disclosure, an active ester compound refers to a compound that has one or more ester groups that react with epoxy groups in one molecule and has the effect of curing epoxy resins.

[0014] Conventionally, phenol curing agents, amine curing agents, etc., are generally used as curing agents for epoxy resins. In the reaction between epoxy resin and phenol curing agents or amine curing agents, secondary hydroxyl groups are generated. In contrast, in the reaction between epoxy resin and active ester compounds, ester groups are generated instead of secondary hydroxyl groups. Since ester groups have lower polarity than secondary hydroxyl groups, the encapsulating resin composition of this disclosure can suppress the dielectric loss tangent of the cured product to a lower level compared to encapsulating resin compositions that contain only curing agents that generate secondary hydroxyl groups.

[0015] Furthermore, the encapsulating resin composition of this disclosure can suppress the dielectric loss tangent of the cured product to a lower level because the average particle size of the inorganic filler it contains is 5 μm or more. Inorganic fillers tend to have a larger specific surface area and a larger amount of surface hydroxyl groups per unit amount as the particle size decreases. By having an average particle size of 5 μm or more of the inorganic filler, the amount of surface hydroxyl groups is reduced, and therefore the amount of hydroxyl groups contained in the cured product of the encapsulating resin composition is reduced, and as a result, the dielectric loss tangent of the cured product can be suppressed to a lower level. On the other hand, from the viewpoint of ensuring the filling properties of the sealing resin composition, the average particle size of the inorganic filler contained in the sealing resin composition of this disclosure is 100 μm or less.

[0016] (Epoxy resin) The type of epoxy resin is not particularly limited as long as it has epoxy groups in its molecule.

[0017] Specifically, the epoxy resins include: novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing a novolac resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing a novolac resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound (benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst; triphenylmethane-type epoxy resins obtained by condensing or co-condensing a triphenylmethane-type phenolic resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound (benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst; and novolac resins obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst. Copolymer epoxy resins that are epoxidized from; diphenylmethane type epoxy resins that are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers of bisphenol S, etc.; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins that are glycidyl esters of polycarboxylic acid compounds 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 replaced with a glycidyl group; dicyclopentadiene type epoxy resins that are epoxidized from a copolymer resin of dicyclopentadiene and a phenol compound;Vinylcyclohexene diepoxide, which is obtained by epoxidizing the olefin bond within the molecule, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; Paraxylylene-modified epoxy resin, which is a glycidyl ether of paraxylylene-modified phenolic resin; Metaxylylene-modified epoxy resin, which is a glycidyl ether of metaxylylene-modified phenolic resin; Terpene-modified epoxy resin, which is a glycidyl ether of terpene-modified phenolic resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenolic resin; Cyclopentadiene-modified epoxy resin, which is a glycidyl ether of cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring-modified epoxy resin, which is a glycidyl ether of polycyclic aromatic ring-modified phenolic resin; Naphthalene-type epoxy resin, which is a glycidyl ether of naphthalene ring-containing phenolic resin; Halogenated phenolic novolak-type epoxy resin; Hydroquinone-type epoxy resin; Trimethylolpropane-type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl-type epoxy resin, which is obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resin and naphthol aralkyl resin; and the like. Further, epoxy compounds of acrylic resins and the like are also cited as epoxy resins. These epoxy resins may be used alone or in combination of two or more kinds.;

[0018] The epoxy equivalent weight (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the 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.

[0019] The epoxy equivalent weight of the epoxy resin shall be the value measured by the method according to JIS K 7236:2009.

[0020] When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of ease of handling during the preparation of the encapsulating resin composition, it is more preferably 50°C to 130°C.

[0021] The melting point or softening point of the epoxy resin shall be the value measured by differential scanning calorimetry (DSC) or by a method (ring-sphere method) in accordance with JIS K 7234:1986.

[0022] The epoxy resin content in the sealing resin composition is preferably 0.5% to 50% by mass, and more preferably 2% to 30% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc.

[0023] (Hardening agent) The encapsulating resin composition of this disclosure contains at least an active ester compound as a curing agent. The encapsulating resin composition of this disclosure may also contain a curing agent other than an active ester compound.

[0024] As described above, the encapsulating resin composition of this disclosure can suppress the dielectric loss tangent of the cured product by using an active ester compound as a curing agent. Furthermore, since polar groups in the cured product increase its water absorption, using an active ester compound as a curing agent can suppress the concentration of polar groups in the cured product, thereby suppressing its water absorption. By suppressing the water absorption of the cured product, that is, by suppressing the content of H2O, a polar molecule, the dielectric loss tangent of the cured product can be further reduced. The water absorption rate of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and even more preferably 0% to 0.25%. Here, the water absorption rate of the cured product is the mass increase rate determined by a pressure cooker test (121°C, 2.1 atm, 24 hours).

[0025] The type of active ester compound is not particularly limited, as long as it is a compound that has one or more ester groups in its molecule that react with epoxy groups.

[0026] Examples of active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified heterocyclic hydroxy compounds.

[0027] Examples of active ester compounds include ester compounds obtained from at least one aliphatic carboxylic acid and an aromatic carboxylic acid, and at least one aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds in which an aliphatic compound is the polycondensation component tend to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain. Ester compounds in which an aromatic compound is the polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring.

[0028] Specific examples of active ester compounds include aromatic esters obtained by the condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups. In particular, aromatic esters obtained by the condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups are preferred, using a mixture of an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with carboxyl groups (such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid), a monovalent phenol in which 1 hydrogen atom of the aforementioned aromatic ring is substituted with a hydroxyl group, and a polyvalent phenol in which 2 to 4 hydrogen atoms of the aforementioned aromatic ring are substituted with hydroxyl groups as raw materials. Specifically, aromatic esters having structural units derived from the above aromatic carboxylic acid component, structural units derived from the above monovalent phenol, and structural units derived from the above polyvalent phenol are preferred.

[0029] Specific examples of active ester compounds include active ester resins having a structure obtained by reacting a phenol resin having a molecular structure in which a phenol compound is bonded via an aliphatic cyclic hydrocarbon group, as described in Japanese Patent Publication No. 2012-246367, with an aromatic dicarboxylic acid or its halide and an aromatic monohydroxy compound. The compound represented by the following structural formula (1) is preferred as the active ester resin.

[0030] [ka]

[0031] In structural formula (1), R 1 X is an alkyl group having 1 to 4 carbon atoms, X is a benzene ring, a naphthalene ring, a benzene or 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 or 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, ranging from 0.25 to 1.5.

[0032] Specific examples of compounds represented by structural formula (1) include the following example compounds (1-1) to (1-10). In the structural formula, t-Bu is a tert-butyl group.

[0033] [ka]

[0034] [ka]

[0035] Other specific examples of active ester compounds include the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3), as described in Japanese Patent Publication No. 2014-114352.

[0036] [ka]

[0037] In structural formula (2), R 1 and R 2Each of the elements is independently a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group, and Z is an ester-forming structural site (z1) selected from the group consisting of a benzoyl group, a naphthoyl group, a benzoyl group or naphthoyl group substituted with a C1-C4 alkyl group, and a C2-C6 acyl group, or a hydrogen atom (z2), and at least one of the elements of Z is an ester-forming structural site (z1).

[0038] In structural formula (3), R 1 and R 2 Each of the elements is independently a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group, and Z is an ester-forming structural site (z1) selected from the group consisting of a benzoyl group, a naphthoyl group, a benzoyl group or naphthoyl group substituted with a C1-C4 alkyl group, and a C2-C6 acyl group, or a hydrogen atom (z2), and at least one of the elements of Z is an ester-forming structural site (z1).

[0039] Specific examples of compounds represented by structural formula (2) include the following example compounds (2-1) to (2-6).

[0040] [ka]

[0041] Specific examples of compounds represented by structural formula (3) include the following example compounds (3-1) to (3-6).

[0042] [ka]

[0043] Commercially available active ester compounds may be used. Examples of commercially available active ester compounds include "EXB9451," "EXB9460," "EXB9460S," and "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK," "EXB-8," and "EXB-9425" (manufactured by DIC Corporation) as active ester compounds containing an aromatic structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolac.

[0044] The active ester compound may be used individually or in combination of two or more compounds.

[0045] The ester group equivalent of the active ester compound is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferred, 170 g / eq to 300 g / eq is more preferred, and 200 g / eq to 250 g / eq is even more preferred.

[0046] The ester group equivalent of the active ester compound shall be the value measured by the method in accordance with JIS K 0070:1992.

[0047] 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 0.9 or higher, more preferably 0.95 or higher, and even more preferably 0.97 or higher. From the viewpoint of minimizing the amount of unreacted active ester compound, the equivalent ratio (ester group / epoxy group) of epoxy resin to active ester compound is preferably 1.1 or less, more preferably 1.05 or less, and even more preferably 1.03 or less.

[0048] The curing agent may include curing agents other than active ester compounds. In this case, the type of other curing agent is not particularly limited and can be selected according to the desired properties of the encapsulating resin composition. Examples of other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymer captan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents.

[0049] Specifically, as phenol curing agents, polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; and compounds synthesized from the above phenolic compounds with dimethoxyp-xylene, bis(methoxymethyl)biphenyl, etc. Examples include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; paraxylylene-modified phenolic resins and metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above 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 phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used individually or in combination of two or more.

[0050] The functional group equivalents of other curing agents (hydroxyl group equivalents in the case of phenol curing agents) are not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, it is preferable that the amount is 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0051] The functional group equivalents of other curing agents (hydroxyl group equivalents in the case of phenol curing agents) shall be values ​​measured according to the method in accordance with JIS K 0070:1992.

[0052] If the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handling during the manufacture of the sealing resin composition, it is more preferably 50°C to 130°C.

[0053] The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0054] The equivalent ratio of epoxy resin to all curing agents (active ester compounds and other curing agents), i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in curing agent / number of functional groups in epoxy resin), is not particularly limited. From the viewpoint of minimizing unreacted components, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is even more preferable to set it in the range of 0.8 to 1.2.

[0055] From the viewpoint of keeping the dielectric loss tangent of the cured product low, 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.

[0056] From the viewpoint of keeping the dielectric loss tangent of the cured product low, the total content of epoxy resin and active ester compound relative to the total mass of epoxy resin, 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.

[0057] (Curing accelerator) The encapsulating resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected according to the type of epoxy resin or curing agent, the desired properties of the encapsulating resin composition, etc.

[0058] Examples of curing accelerators 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; and phenol novolac salts of the cyclic amidine compounds or their derivatives. Compounds having intramolecular polarization obtained by adding compounds with π bonds to these compounds, such as maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and other quinone compounds, and diazophenylmethane; tetraphenylmethane of DBU Compounds obtained by adding isocyanates to cyclic amidinium compounds such as nylborate salts, tetraphenylborate salt of DBN, tetraphenylborate salt of 2-ethyl-4-methylimidazole, and tetraphenylborate salt 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;Triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl·alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkoxy Tertiary phosphines such as diarylphosphines and alkyldiarylphosphines; phosphine compounds such as complexes of the tertiary phosphine with organoborons; quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and diazophenylmethane. Compounds having intramolecular polarization, such as those obtained by adding compounds having π bonds; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodidephenol, 3-iodidephenol, 2-iodidephenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di- Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl, followed by a dehalogenation step; tetrasubstituted phosphoniums such as tetraphenylphosphonium, tetrasubstituted phosphoniums and tetrasubstituted borates that lack a phenyl group bonded to the boron atom, such as tetra-p-tolylborate; salts of tetraphenylphosphonium and phenol compounds;Examples include salts of tetraalkylphosphonium and partially hydrolyzed aromatic carboxylic acid anhydrides.

[0059] When the sealing resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). When the amount of curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin component, it tends to result in a good molded product with a curing speed that is not too fast.

[0060] (Inorganic filler) The encapsulating resin composition of this disclosure has an average particle size of inorganic filler material of 5 μm to 100 μm. From the viewpoint of reducing the amount of surface hydroxyl groups per unit amount and, as a result, keeping the dielectric loss tangent of the cured product low, the average particle size of the inorganic filler material is preferably 5 μm or more, 8 μm or more, and more preferably 10 μm or more. From the viewpoint of improving the filling properties of the encapsulating resin composition, the average particle size of the inorganic filler material is preferably 100 μm or less, 50 μm or less, and more preferably 20 μm or less.

[0061] The average particle size of the inorganic filler is determined by measuring the major axis of 100 randomly selected inorganic fillers in images of thin slices of the sealing resin composition or its cured product, taken with a scanning electron microscope, and then arithmetically averaging these measurements.

[0062] The type of inorganic filler is not particularly limited. Specifically, 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 magnesium and zinc hydroxide, and zinc borate.

[0063] Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the coefficient of thermal expansion, 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. Examples of inorganic filler forms include powder, beads formed from spherical powder, and fibers.

[0064] The content of inorganic filler in the encapsulating resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% to 90% by volume of the total encapsulating resin composition, more preferably 35% to 80% by volume, and even more preferably 40% to 70% by volume. When the inorganic filler content is 30% or more by volume of the total encapsulating resin composition, the properties of the cured product, such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus, tend to improve further. When the inorganic filler content is 90% or less by volume of the total encapsulating resin composition, the increase in viscosity of the encapsulating resin composition is suppressed, fluidity improves further, and moldability tends to be better.

[0065] [Various additives] In addition to the components described above, the sealing resin composition may also contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, and colorants, as exemplified below. The sealing resin composition may also contain, as necessary, various additives well known in the art, in addition to those exemplified below.

[0066] (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, it is preferable that the encapsulating resin composition contains a coupling agent. Examples of known coupling agents include silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, as well as titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0067] When the resin composition for sealing contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass, based on 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more based on 100 parts by mass of the inorganic filler, the adhesion to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

[0068] (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 the element to be sealed, the resin composition for sealing preferably contains an ion exchanger. The ion exchanger is not particularly limited, and a conventionally known one can be used. Specifically, examples include hydrotalcite compounds and hydrated oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0069] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≦ 0.5, m is a positive number)

[0070] When the resin composition for sealing contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin component (total amount of the epoxy resin and the curing agent).

[0071] (Release agent) The sealing resin composition may contain a release agent to obtain good release properties from the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more types.

[0072] If the sealing resin composition contains a release agent, the amount is preferably 0.01 to 10 parts by mass, and 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 release agent is 0.01 parts by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When it is 10 parts by mass or less, better adhesion tends to be obtained.

[0073] (Flame retardant) The sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specifically, examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardant may be used alone or in combination of two or more types.

[0074] If the sealing resin composition contains a flame retardant, the amount is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

[0075] (Coloring agent) The sealing resin composition may contain a coloring agent. Examples of known coloring agents include carbon black, organic dyes, organic pigments, titanium dioxide, red lead, and red iron oxide. The amount of coloring agent can be appropriately selected depending on the purpose. One coloring agent may be used alone, or two or more coloring agents may be used in combination.

[0076] (Method for preparing a encapsulating resin composition) The method for preparing the encapsulating resin composition is not particularly limited. A common method involves thoroughly mixing predetermined amounts of components using a mixer or the like, then melt-kneading them using a mixing roll, extruder, or the like, followed by cooling and pulverization. More specifically, for example, a method can be used in which predetermined amounts of the above-mentioned components are uniformly stirred and mixed, then kneaded using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, followed by cooling and pulverization.

[0077] The sealing resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25°C and atmospheric pressure). The shape of the sealing resin composition when it is solid is not particularly limited and can be in powder, granular, or tablet form. When the sealing resin composition is in tablet form, its dimensions and mass are preferably such that they are suitable for the packaging molding conditions, from the viewpoint of ease of handling.

[0078] <Electronic Components and Devices> An electronic component device according to one embodiment of the present disclosure comprises a support member, an element disposed on the support member, and a cured product of the sealing resin composition of the present disclosure that seals the element.

[0079] Examples of electronic component devices include those in which elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) are mounted on support members such as lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, and the resulting element section is sealed with a sealing resin composition. More specifically, common resin-encapsulated ICs such as DIP (Dual Inline Package), 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) have a structure in which elements are fixed on a lead frame, the terminal parts of the elements such as bonding pads are connected to the lead parts by wire bonding, bumps, etc., and then encapsulated using a sealing resin composition by transfer molding, etc.; TCP (Tape Carrier Package) has a structure in which elements connected to a tape carrier by bumps are encapsulated with a sealing resin composition; and COB (Chip On) has a structure in which elements are connected to wiring formed on a support member by wire bonding, flip-chip bonding, solder, etc., and then encapsulated with a sealing resin composition. Examples of such modules include boards, hybrid ICs, and multi-chip modules; BGAs (Ball Grid Arrays), CSPs (Chip Size Packages), and MCPs (Multi Chip Packages) which have a structure in which elements are mounted on the surface of a support member having terminals for connecting to a wiring board formed on the back surface, the elements are connected to the wiring formed on the support member by bump or wire bonding, and then the elements are sealed with a sealing resin composition. Furthermore, sealing resin compositions can also be suitably used in printed wiring boards.

[0080] <Manufacturing method for electronic component devices> A method for manufacturing an electronic component device according to the present disclosure includes the steps of arranging an element on a support member and sealing the element with a sealing resin composition according to the present disclosure.

[0081] The method for carrying out each of the above steps is not particularly limited and can be carried out using general methods. Furthermore, the types of support members and elements used in the manufacture of electronic component devices are not particularly limited and can be those commonly used in the manufacture of electronic component devices.

[0082] Methods for encapsulating elements using the encapsulating resin composition of this disclosure include low-pressure transfer molding, injection molding, and compression molding. Among these, low-pressure transfer molding is the most common. [Examples]

[0083] The above embodiments will be described in detail below with reference to examples, but the scope of the above embodiments is not limited to these examples.

[0084] <Preparation of encapsulating resin composition> The components listed below were mixed in the proportions shown in Table 1 to prepare the sealing resin compositions for the examples and comparative examples. These sealing resin compositions were solid at room temperature and pressure.

[0085] • Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000") • Epoxy resin 2: Dicyclopentadiene type epoxy resin, epoxy equivalent 258 g / eq (DIC Corporation, product name "HP-7200") • Epoxy resin 3: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60") • Epoxy resin 4: Biphenyl-type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

[0086] • Active ester compound 1: DIC Corporation, product name "EXB-8" • Phenolic curing agent 1: Phenolic aralkyl resin, hydroxyl group equivalent 175g / eq (Meiwa Chemicals Co., Ltd., product name "MEH7800SS")

[0087] • Curing accelerator 1: Triphenylphosphine / 1,4-benzoquinone adduct

[0088] • Filler 1: Fused silica (DENKA Corporation, product name "FB-870FD") • Filler 2: Fused silica (Takimori Co., Ltd., product name "EUF-46V") • Filler 3: Fused silica (Takimori Co., Ltd., product name "MUF-2BV") • Filler 4: Fused silica (Admatex Co., Ltd., product name "SO-25R")

[0089] • 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: Montane ester wax (Clariant Japan Co., Ltd., product name "HW-E") • Coloring agent: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")

[0090] <Performance evaluation of encapsulating resin compositions> (Average particle size of inorganic filler) In images of thin sections of the sealing resin composition captured with a scanning electron microscope, the major axis (μm) of 100 randomly selected inorganic fillers was measured, and the arithmetic mean was calculated.

[0091] (Spiral Flow) Using a spiral flow measurement mold conforming to EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance (cm) was determined.

[0092] (Relative permittivity and dielectric loss tangent) The sealing resin composition was placed in a vacuum hand press machine and molded under the following conditions: mold temperature 175°C, molding pressure 6.9 MPa, curing time 600 seconds. Post-curing was carried out at 180°C for 6 hours to obtain a plate-shaped cured material (12.5 mm long, 25 mm wide, 0.2 mm thick). Using this plate-shaped cured material as a test piece, the relative permittivity and dielectric loss tangent were measured at a temperature of 25 ± 3°C and approximately 60 GHz using a dielectric constant measuring device (Agilent Technologies, product name "Network Analyzer N5227A").

[0093] (Water absorption rate) The plate-shaped hardened material described above, immediately after manufacturing, was placed in a pressure cooker test apparatus at 121°C / 2.1 atmospheres. After 24 hours, it was removed, and the percentage increase in mass from the mass immediately before placement was determined.

[0094] [Table 1]

[0095] All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. It contains epoxy resin, a hardener, and an inorganic filler. The curing agent contains an active ester compound, A sealing resin composition wherein the average particle size of the inorganic filler is 5 μm to 100 μm.

2. Support member and The element arranged on the support member, A cured product of the sealing resin composition according to claim 1, which seals the element, An electronic component device equipped with the following features.

3. A step of placing the element on a support member, The steps include sealing the element with the sealing resin composition described in claim 1, A method for manufacturing an electronic component device that includes [specific component].

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