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

Abstract

The invention relates to a resin composition for sealing, an electronic component device, and a method for manufacturing the electronic component device. A resin composition for sealing, which is used for narrow path filling and contains an epoxy resin, a curing agent, and an inorganic filler, the curing agent containing an active ester compound, and the inorganic filler having an average particle diameter of less than 10 [mu] m.

Description

[0001] This application is a divisional application. The filing date of the parent application is September 27, 2018. The international application number is PCT / JP2018 / 036100. The application number entering the Chinese national phase is 201880098074.X. The name of the invention is sealing resin composition, electronic component device and method for manufacturing electronic component device. Technical Field

[0002] The present invention relates to a sealing resin composition, an electronic component device, and a method for producing an electronic component device. Background Art

[0003] The amount of transmission loss caused by the heat conversion of radio waves sent for communication in the dielectric is expressed as the product of the frequency, the square root of the relative dielectric constant and the dielectric loss tangent. In other words, the transmission signal is easily converted into heat in proportion to the frequency. Therefore, in order to suppress the transmission loss, the higher the frequency band, the lower the dielectric properties required for the materials of the communication components.

[0004] For example, Patent Documents 1 and 2 disclose thermosetting resin compositions containing an active ester resin as a curing agent for epoxy resins, and thereby the dielectric loss tangent of the cured product can be suppressed to be low.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-246367

[0008] Patent Document 2: Japanese Patent Application Publication No. 2014-114352 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In the field of information communication, with the increase in the number of channels and the amount of information transmitted, the high frequency of radio waves is developing. Currently, research on the fifth generation mobile communication system is being carried out worldwide, and several frequency bands in the range of about 30 GHz to 70 GHz can be cited as candidates for the frequency bands used. In the future, the mainstream of wireless communication will become communication in such high frequency bands, so the dielectric loss tangent of the materials of communication components is required to be lower.

[0011] Furthermore, as semiconductor devices become smaller, thinner, lighter, or more highly functional, when the bump pitch or the interval between elements is narrowed, a sealing resin composition having excellent narrow path filling properties is required.

[0012] The embodiments of the present disclosure have been completed based on the above-mentioned circumstances.

[0013] An object of the present disclosure is to provide a sealing resin composition having excellent narrow path filling properties and a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and a method for producing an electronic component device sealed using the same.

[0014] Means for solving problems

[0015] Specific means for solving the above-mentioned problems include the following aspects.

[0016] [1] A sealing resin composition for use in narrow road filling, the sealing resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein the curing agent comprises an active ester compound, and the average particle size of the inorganic filler is less than 10 μm.

[0017] [2] The sealing resin composition according to [1], wherein the maximum particle size of the inorganic filler is less than 20 μm.

[0018] [3] The sealing resin composition according to [1] or [2], which is used for mold bottom filling.

[0019] [4] An electronic component device comprising: a support member; a device disposed on the support member; and a cured product of the sealing resin composition according to any one of [1] to [3] that fills a narrow path around the device.

[0020] [5] A method for manufacturing an electronic component device, comprising: placing an element on a support member; and filling a narrow path around the element with the sealing resin composition according to any one of [1] to [3].

[0021] Effects of the Invention

[0022] According to the present disclosure, there are provided a sealing resin composition having excellent narrow path filling properties and a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and a method for producing an electronic component device sealed using the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a top view (partial perspective view) illustrating a test chip used in the examples.

[0024] Figure 2 This is a cross-sectional view illustrating a test chip used in Examples. DETAILED DESCRIPTION

[0025] In the present disclosure, the term "process" includes processes that are independent of other processes and processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved.

[0026] In the present disclosure, when a numerical range is expressed using "to", the numerical values ​​described before and after "to" are included as the minimum value and the maximum value, respectively.

[0027] In the numerical ranges recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in the present disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment.

[0028] In the present disclosure, each component may include a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the plurality of substances present in the composition.

[0029] In the present disclosure, particles corresponding to each component may include multiple types. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to the value for the mixture of the multiple types of particles present in the composition unless otherwise specified.

[0030] In the present disclosure, when the embodiments are described with reference to the drawings, the configuration of the embodiments is not limited to the configuration shown in the drawings. In addition, the sizes of the components in each figure are conceptual, and the relative relationship between the sizes of the components is not limited to this.

[0031] <Sealing resin composition>

[0032] The sealing resin composition disclosed in the present invention is used for narrow road filling. The sealing resin composition contains epoxy resin, curing agent and inorganic filler. The curing agent contains active ester compound. The average particle size of the inorganic filler is less than 10 μm.

[0033] The narrow path using the sealing resin composition of the present disclosure refers to a gap having at least one of a height or a width of 100 μm or less. Examples of the narrow path include a gap between a supporting member and an element, and a gap between adjacent elements.

[0034] The sealing resin composition of the present disclosure may be used to fill a narrow path included in an electronic component device and to seal a part of a space other than the narrow path in the electronic component device or the entire electronic component device.

[0035] Examples of the above-mentioned embodiments include a sealing resin composition for mold underfill (MUF) for sealing a component disposed on a supporting member and filling a gap between the supporting member and the component, and a sealing resin composition for SiP (system in a package).

[0036] The active ester compound in the present disclosure refers to a compound having one or more ester groups reactive with an epoxy group in one molecule and having a curing effect on an epoxy resin.

[0037] In the past, as the curing agent of epoxy resin, phenol curing agent, amine curing agent etc. were usually used, but secondary hydroxyl was produced in the reaction of epoxy resin and phenol curing agent or amine curing agent. In contrast, in the reaction of epoxy resin and active ester compound, ester group is produced instead of secondary hydroxyl. Ester group has lower polarity than secondary hydroxyl, therefore, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of cured product to be low compared with the sealing resin composition of curing agent containing only the curing agent producing secondary hydroxyl.

[0038] Furthermore, the sealing resin composition of the present disclosure has excellent narrow path filling properties because the inorganic filler contained therein has an average particle size of less than 10 μm. The reason for this is presumably that the inorganic filler is less likely to clog the narrow path when the melt of the sealing resin composition flows through the narrow path.

[0039] In the sealing 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 fillers.

[0040] (Epoxy resin)

[0041] The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.

[0042] Epoxy resins include, specifically, epoxy resins obtained by epoxidizing a novolac resin obtained by condensing or co-condensing a phenolic compound with an aliphatic aldehyde compound under an acidic catalyst, i.e., novolac epoxy resins (phenol novolac epoxy resins, o-cresol novolac epoxy resins, etc.), wherein the phenolic compound is at least one selected from phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and the aliphatic aldehyde compound is formaldehyde, acetaldehyde, propionaldehyde, etc.; and triphenylmethane obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst. epoxidized epoxy resins of triphenylmethane type phenolic resins; epoxy resins of linear phenolic resins obtained by epoxidizing the above-mentioned phenolic compounds and naphthol compounds with aldehyde compounds under an acidic catalyst, i.e. copolymerized epoxy resins; diglycidyl ethers of bisphenol A, bisphenol F, etc., i.e. diphenylmethane type epoxy resins; diglycidyl ethers of alkyl-substituted or unsubstituted biphenols, i.e. biphenyl type epoxy resins; diglycidyl ethers of stilbene-based phenol compounds, i.e. stilbene type epoxy resins; diglycidyl ethers of bisphenol S, etc., i.e. epoxy resins containing sulfur atoms; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; phthalic acid, isophthalic acid, tetrahydrophthalic acid, glycidyl esters of polycarboxylic acid compounds such as oxalic acid, i.e. glycidyl ester type epoxy resins; epoxy resins obtained by substituting active hydrogen bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with glycidyl groups, i.e. glycidylamine type epoxy resins; epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound, i.e. dicyclopentadiene type epoxy resins; epoxy resins obtained by epoxidizing olefinic bonds in the molecule, such as vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc.; glycidyl ethers of p-xylene-modified phenolic resins , namely, p-xylene modified epoxy resin; glycidyl ether of m-xylene modified phenolic resin, namely, m-xylene modified epoxy resin; glycidyl ether of terpene modified phenolic resin, namely, terpene modified epoxy resin; glycidyl ether of dicyclopentadiene modified phenolic resin, namely, dicyclopentadiene modified epoxy resin; glycidyl ether of cyclopentadiene modified phenolic resin, namely, cyclopentadiene modified epoxy resin; glycidyl ether of polycyclic aromatic ring modified phenolic resin, namely, polycyclic aromatic ring modified epoxy resin; glycidyl ether of phenolic resin containing naphthalene ring, namely, naphthalene type epoxy resin; halogenated phenol linear phenolic type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracids such as peracetic acid;Epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins, i.e., aralkyl-type epoxy resins; etc. In addition, epoxides of acrylic resins and the like can also be cited as epoxy resins. These epoxy resins can be used alone or in combination of two or more. ;

[0043] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited, but is preferably 100 g / eq to 1000 g / eq, more preferably 150 g / eq to 500 g / eq, from the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability.

[0044] The epoxy equivalent of the epoxy resin is set to a value measured by a method in accordance with JIS K 7236:2009.

[0045] 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 when preparing the sealing resin composition.

[0046] The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) in accordance with JIS K 7234:1986.

[0047] From the viewpoints of strength, fluidity, heat resistance, moldability, and the like, the content of the epoxy resin in the sealing resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass.

[0048] (Curing agent)

[0049] The sealing resin composition of the present disclosure contains at least an active ester compound as a curing agent. The sealing resin composition of the present disclosure may contain a curing agent other than the active ester compound.

[0050] As described above, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to be low by using an active ester compound as a curing agent.

[0051] In addition, the polar groups in the cured product increase the water absorption of the cured product. By using an active ester compound as a curing agent, the concentration of polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. In addition, by suppressing the water absorption of the cured product, that is, suppressing the H as a polar molecule 2The content of O can suppress the dielectric loss tangent of the cured product to a lower level. The water absorption of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and further preferably 0% to 0.25%. Here, the water absorption of the cured product is the mass increase rate obtained by the pressure cooker cooking test (121°C, 2.1 atmospheres, 24 hours).

[0052] The type of the active ester compound is not particularly limited as long as it is a compound having one or more ester groups reactive with an epoxy group in the molecule.

[0053] Examples of the active ester compound include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esters of heterocyclic hydroxy compounds.

[0054] Examples of the active ester compound include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxyl compound and an aromatic hydroxyl compound. An ester compound having an aliphatic compound as a polycondensation component tends to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain. An ester compound having an aromatic compound as a polycondensation component tends to have excellent heat resistance due to the presence of an aromatic ring.

[0055] As a specific example of the active ester compound, there can be mentioned an aromatic ester obtained by a condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group. Among them, preferred is an aromatic ester obtained by a condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group using a mixture of an aromatic carboxylic acid component, a monohydric phenol and a polyhydric phenol as raw materials, wherein the aromatic carboxylic acid component is a compound in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfonic acid are substituted with carboxyl groups, the monohydric phenol is a compound in which 1 hydrogen atom of the aromatic ring is substituted with a hydroxyl group, and the polyhydric phenol is a compound in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with hydroxyl groups. That is, it is preferred to have a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monohydric phenol and a structural unit derived from the polyhydric phenol.

[0056] Specific examples of active ester compounds include active ester resins described in Japanese Patent Application Laid-Open No. 2012-246367, which are obtained by reacting a phenolic resin, an aromatic dicarboxylic acid or a halide thereof, and an aromatic monohydroxy compound, wherein the phenolic resin has a molecular structure in which a phenol compound is bonded via an aliphatic cyclic hydrocarbon group. As the active ester resin, a compound represented by the following structural formula (1) is preferred.

[0057] [Chemical formula 1]

[0058]

[0059] In the 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 represents the average number of repetitions, which is 0.25 to 1.5.

[0060] Specific examples of the compound represented by the structural formula (1) include the following exemplary compounds (1-1) to (1-10): t-Bu in the structural formula is a tert-butyl group.

[0061] [Chemical formula 2]

[0062]

[0063] [Chemical formula 3]

[0064]

[0065] Another specific example of the active ester compound includes a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3) described in JP-A-2014-114352.

[0066] [Chemical formula 4]

[0067]

[0068] In the structural formula (2), R 1 and R 2 Each is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, Z is an ester-forming structural site (z1) selected from 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 site (z1).

[0069] In the structural formula (3), R 1 and R 2 Each is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, Z is an ester-forming structural site (z1) selected from 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 site (z1).

[0070] Specific examples of the compound represented by the structural formula (2) include the following exemplary compounds (2-1) to (2-6).

[0071] [Chemical formula 6]

[0072]

[0073] Specific examples of the compound represented by the structural formula (3) include the following exemplary compounds (3-1) to (3-6).

[0074] [Chemical formula 7]

[0075]

[0076] As the active ester compound, a commercially available product can be used. As for the commercially available products as active ester compounds, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation) can be cited; as active ester compounds containing an aromatic structure, "EXB9416-70BK", "EXB-8", and "EXB-9425" (manufactured by DIC Corporation) can be cited; as active ester compounds containing an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) can be cited; as active ester compounds containing a benzoylated product of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) can be cited.

[0077] The active ester compound may be used alone or in combination of two or more.

[0078] The ester equivalent of the active ester compound is not particularly limited, but is preferably 150 g / eq to 400 g / eq, more preferably 170 g / eq to 300 g / eq, and even more preferably 200 g / eq to 250 g / eq from the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability.

[0079] The ester group equivalent of the active ester compound is set to a value measured by a method in accordance with JIS K 0070:1992.

[0080] From the viewpoint of suppressing the dielectric loss tangent of the cured product to be low, the equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 0.9 or more, more preferably 0.95 or more, and even more preferably 0.97 or more.

[0081] From the viewpoint of reducing the unreacted components of the active ester compound, 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.

[0082] The curing agent may include other curing agents other than the active ester compound. In this case, the type of other curing agents is not particularly limited and can be selected according to the desired properties of the sealing resin composition. As other curing agents, phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. can be cited.

[0083] As the phenol curing agent, specifically, there can be mentioned: polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenols; linear phenolic resins obtained by condensing or co-condensing phenolic compounds with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst, wherein the phenolic compound is at least one selected from phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc.; and phenolic resins synthesized from the above phenolic compounds with dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. Aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; p-xylene-modified phenolic resins and m-xylene-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 condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenolic resins obtained by copolymerizing two or more of these; etc. These phenolic curing agents can be used alone or in combination of two or more.

[0084] The functional group equivalent of other curing agents (hydroxyl equivalent in the case of phenolic curing agents) is not particularly limited, but is preferably 70 g / eq to 1000 g / eq, more preferably 80 g / eq to 500 g / eq, from the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability.

[0085] The functional group equivalent of other curing agents (hydroxyl group equivalent in the case of a phenol curing agent) is set to a value measured by a method in accordance with JIS K0070:1992.

[0086] When the curing agent is solid, the 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 when producing the sealing resin composition.

[0087] The melting point or softening point of the curing agent is set to a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0088] The equivalent ratio of the epoxy resin to the total curing agent (active ester compound and other curing agents), that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (the number of functional groups in the curing agent / the number of functional groups in the epoxy resin) is not particularly limited. From the viewpoint of suppressing the respective unreacted components to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is further preferably set in the range of 0.8 to 1.2.

[0089] From the viewpoint of suppressing the dielectric loss tangent of the cured product to be 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 mass % or more, more preferably 85 mass % or more, and even more preferably 90 mass % or more.

[0090] From the viewpoint of suppressing the dielectric loss tangent of the cured product to be low, 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.

[0091] (Curing accelerator)

[0092] The sealing resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and can be selected according to the type of the epoxy resin or the curing agent, the desired properties of the sealing resin composition, and the like.

[0093] Examples of the curing accelerator include diazabicycloolefins 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 above cyclic amidine compounds; phenol phenolate salts of the above cyclic amidine compounds or their derivatives; and addition of maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethylbenzoquinone, and the like to these compounds. Compounds with intramolecular polarization formed by quinone compounds such as methoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having π bonds such as diazonophenylmethane; compounds formed by adding isocyanates to cyclic amidine compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, and tetraphenylborate of N-methylmorpholine; isocyanate adducts of DBU, isocyanate adducts of DBN, isocyanate adducts of 2-ethyl-4-methylimidazole, and N- Isocyanate adducts of methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, 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, tetrapropylammonium hydroxide; triphenylphosphine, diphenyl(p-tolyl)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl·alkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine )phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine and other tertiary phosphines; phosphine compounds such as complexes of the above tertiary phosphines and organic boron; compounds with intramolecular polarization formed by the addition of the above tertiary phosphine or the above phosphine compound with maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, compounds having π bonds such as diazonophenylmethane;The above tertiary phosphine or the above phosphine compound 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, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthalene Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as phenol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc., and then undergoing a dehydrohalogenation process; tetrasubstituted phosphoniums such as tetraphenylphosphonium, tetra-p-tolyl borate, etc., tetrasubstituted phosphoniums and tetrasubstituted borates that do not have a phenyl group bonded to a boron atom; salts of tetraphenylphosphonium and phenol compounds; salts of tetraalkylphosphonium and partial hydrolyzates of aromatic carboxylic anhydrides, etc.;

[0094] When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent). If the amount of the curing accelerator is 0.1 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to cure well in a short time. If the amount of the curing accelerator is 30 parts by mass or less relative to 100 parts by mass of the resin component, there is a tendency that the curing speed will not be too fast and a good molded product can be obtained.

[0095] (Inorganic filling materials)

[0096] In the sealing resin composition disclosed herein, the average particle size of the inorganic filler contained is less than 10 μm. From the viewpoint of improving narrow path filling performance, the average particle size of the inorganic filler is less than 10 μm, preferably less than 9 μm. From the viewpoint of suppressing the aggregation of the inorganic fillers, the average particle size of the inorganic filler is preferably 3 μm or more, more preferably 5 μm or more.

[0097] From the viewpoint of further improving the narrow path filling property, the maximum particle size of the inorganic filler contained in the sealing resin composition of the present disclosure is preferably less than 30 μm, more preferably less than 25 μm, and even more preferably less than 20 μm.

[0098] The average particle size of the inorganic filler is the value obtained by measuring the major diameters of 100 randomly selected inorganic fillers in an image obtained by photographing a thin slice sample of the sealing resin composition or its cured product using a scanning electron microscope, and calculating the arithmetic average thereof. The maximum particle size of the inorganic filler is the maximum value among the above 100 major diameters.

[0099] There is no particular restriction on the type of inorganic filler. Specifically, inorganic materials such as fused silica, crystalline silica, glass, aluminum oxide, talc, clay, and mica can be cited. Inorganic fillers with flame retardant effects can also be used. As inorganic fillers with flame retardant effects, composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate can be cited.

[0100] Among the inorganic fillers, from the viewpoint of reducing the linear expansion coefficient, preferably silicon dioxide such as fused silica, from the viewpoint of high thermal conductivity, preferably aluminum oxide. One inorganic filler can be used alone, or two or more can be used in combination. As the form of the inorganic filler, powder, beads obtained by sphericalizing the powder, fibers, etc. can be cited.

[0101] The content of the inorganic filler contained in the sealing resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% to 90% by volume of the entire sealing resin composition, more preferably 35% to 80% by volume, and further preferably 40% to 70% by volume. If the content of the inorganic filler is more than 30% by volume of the entire sealing resin composition, there is a trend that the thermal expansion coefficient, thermal conductivity, elastic modulus and other characteristics of the cured product are further improved. If the content of the inorganic filler is less than 90% by volume of the entire sealing resin composition, the rise in the viscosity of the sealing resin composition is suppressed, and fluidity is further improved, and there is a trend that the formability becomes better.

[0102] [Various additives]

[0103] The sealing resin composition may contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, etc., in addition to the above components. The sealing resin composition may contain various additives known in the art, in addition to the additives exemplified below.

[0104] (Coupling agent)

[0105] The sealing resin composition may contain a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. As the coupling agent, there can be mentioned: silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, urea silane, vinyl silane, disilazane, titanium compounds, aluminum chelate compounds, aluminum / zirconium compounds and the like known coupling agents.

[0106] When the sealing 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, relative to 100 parts by mass of the inorganic filler. If the amount of the coupling agent is 0.05 parts by mass or more relative to 100 parts by mass of the inorganic filler, there is a tendency for the adhesion to the frame to be further improved. If the amount of the coupling agent is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, there is a tendency for the formability of the package to be further improved.

[0107] (Ion exchanger)

[0108] The sealing resin composition may contain an ion exchanger. From the viewpoint of improving the moisture resistance and high temperature storage characteristics of the electronic component device having the element to be sealed, the sealing resin composition preferably contains an ion exchanger. There is no particular limitation on the ion exchanger, and conventionally known ion exchangers can be used. Specifically, hydrotalcite compounds and hydrous oxides of at least one element selected from magnesium, aluminum, titanium, zirconium and bismuth can be cited. The ion exchanger can be used alone or in combination of two or more. Among them, the hydrotalcite represented by the following general formula (A) is preferred.

[0109] Mg （1-X） Al X (OH) 2 (CO 3 ) X / 2 ·mH 2 O……(A)

[0110] (0<X≤0.5, m is a positive number)

[0111] When the sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient for capturing halogen ions and the like, for example, preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the resin component (total amount of the epoxy resin curing agent).

[0112] (Release agent)

[0113] From the viewpoint of obtaining good demoulding property with the mold when forming, the sealing resin composition may include a release agent. The release agent is not particularly limited, and a previously known release agent can be used. Specifically, ester waxes such as carnauba wax, montanic acid, stearic acid and other higher fatty acids, higher fatty acid metal salts, montanic acid esters, oxidized polyethylene, non-oxidized polyethylene and other polyolefin waxes can be cited. The release agent can be used alone or in combination of two or more.

[0114] When the sealing resin composition contains a release agent, the amount thereof is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent). If the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to obtain sufficient releasability. If it is 10 parts by mass or less, there is a tendency to obtain better adhesion.

[0115] (Flame retardant)

[0116] The sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants may be used. Specifically, organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. may be mentioned. The flame retardant may be used alone or in combination of two or more.

[0117] When the sealing 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, it is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent).

[0118] (Colorant)

[0119] The sealing resin composition may contain a colorant. As the colorant, known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron can be cited. The content of the colorant can be appropriately selected according to the purpose, etc. The colorant can be used alone or in combination of two or more.

[0120] (Method for preparing sealing resin composition)

[0121] The preparation method of the sealing resin composition is not particularly limited. As a common method, there can be mentioned a method in which the components of the prescribed amount are fully mixed by a mixer, etc., and then melt-kneaded, cooled, and crushed by a grinding roll, an extruder, etc. More specifically, for example, there can be mentioned a method in which the prescribed amount of the above-mentioned components is uniformly stirred and mixed, and then kneaded, cooled, and crushed by a kneader, a roll, an extruder, etc. preheated to 70°C to 140°C.

[0122] The sealing resin composition is preferably solid at room temperature and pressure (e.g., 25° C., atmospheric pressure). The shape of the sealing resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, and sheets. From the viewpoint of handling, the size and mass of the sealing resin composition when it is in sheet form are preferably such that they meet the molding conditions of the package.

[0123] <Electronic components and devices>

[0124] An electronic component device as one embodiment of the present disclosure includes a supporting member, an element disposed on the supporting member, and a cured product of the sealing resin composition of the present disclosure that fills a narrow path around the element.

[0125] An electronic component device as one embodiment of the present disclosure has a narrow path filled with a sealing resin composition of the present disclosure. Examples of the narrow path include a gap between a support member and an element, a gap between adjacent elements, and the like. An electronic component device as one embodiment of the present disclosure can be sealed with a portion or the entirety other than the narrow path using the sealing resin composition of the present disclosure.

[0126] Examples of electronic component devices include devices in which a component portion (active components such as semiconductor chips, transistors, diodes, thyristors, etc., passive components such as capacitors, resistors, coils, etc.) is mounted on a supporting member such as a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, an organic substrate, etc., and sealed with a sealing resin composition.

[0127] More specifically, there can be mentioned conventional resin-sealed 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), which have a structure in which a component is fixed to a lead frame, a terminal portion of the component such as a bonding pad and a lead portion are connected by wire bonding, bumps, etc., and then sealed using a sealing resin composition by transfer molding or the like; TCP (Tape Carrier Package) having a structure in which a component connected to a tape carrier by bumps is sealed with a sealing resin composition; COB (Chip On Board) Board: chip on board package) modules, hybrid ICs, multi-chip modules, etc., which have the following structure, that is, the components connected to the wiring formed on the supporting member by wire bonding, flip chip bonding, solder, etc. are sealed with a sealing resin composition; BGA (Ball Grid Array: ball grid array package), CSP (Chip Size Package: chip size package), MCP (Multi Chip Package: multi-chip package), which have the following structure, that is, the components are mounted on the surface of a supporting member having terminals for connecting to a wiring board formed on the back, and the components are connected to the wiring formed on the supporting member by bumps or wire bonding, and then the components are sealed with a sealing resin composition; SiP (system in a package: system-level package) in which multiple components are sealed in one package, etc.

[0128] <Method for manufacturing electronic component device>

[0129] The method for manufacturing an electronic component device of the present disclosure includes the steps of placing an element on a supporting member and filling a narrow path around the element with the sealing resin composition of the present disclosure.

[0130] There is no particular limitation on the method of implementing each of the above steps, and the steps may be carried out by a common method. In addition, there is no particular limitation on the types of support members and elements used in the manufacture of electronic component devices, and support members and elements commonly used in the manufacture of electronic component devices may be used.

[0131] The step of filling the narrow path around the component with the sealing resin composition of the present disclosure may be a step of simultaneously filling the narrow path around the component and sealing a part of the space other than the narrow path in the electronic component device or the entire electronic component device.

[0132] Examples of a method for filling a narrow path around a component using the sealing resin composition of the present disclosure include low-pressure transfer molding, injection molding, compression molding, etc. Among them, low-pressure transfer molding is common.

[0133] Example

[0134] Hereinafter, the above-described embodiment will be specifically described by way of examples, but the scope of the above-described embodiment is not limited to these examples.

[0135] <Preparation of Sealing Resin Composition>

[0136] The sealing resin compositions of Examples and Comparative Examples were prepared by mixing the following components in the proportions shown in Table 1. The sealing resin compositions are solid at normal temperature and pressure.

[0137] Epoxy resin 1: biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., trade name "NC-3000")

[0138] Epoxy resin 2: triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Co., Ltd., trade name "1032H60")

[0139] Epoxy resin 3: biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Co., Ltd., trade name "YX-4000")

[0140] Active ester compound 1: DIC Corporation, trade name "EXB-8"

[0141] Active ester compound 2: DIC Corporation, trade name "EXB-9425"

[0142] Phenol curing agent 1: phenol aralkyl resin, hydroxyl equivalent 175 g / eq (Meiwa Chemicals Co., Ltd., trade name "MEH7800SS")

[0143] Curing accelerator 1: triphenylphosphine / 1,4-benzoquinone adduct

[0144] Curing accelerator 2: Imidazole compound (Shikoku Chemical Industry Co., Ltd., trade name "CUREZOL 2E4MZ")

[0145] Filler 1: Fused silica (DENKA, trade name "FB-310MDC")

[0146] Filler 2: Fused silica (Micron, trade name "ST7010-2")

[0147] Filler 3: Fused silica (Admatechs, trade name "SO-25R")

[0148] Filler 4: Fused silica (DENKA, trade name "FB-9454FC")

[0149] Filler 5: Fused silica (Micron, trade name "ST7010-3")

[0150] · Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name "KBM-573")

[0151] Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name "KBM-803")

[0152] Release agent: montanic acid ester wax (Clariant Japan Co., Ltd., trade name "HW-E")

[0153] Colorant: Carbon black (Mitsubishi Chemical Co., Ltd., trade name "MA600")

[0154] <Evaluation of performance of sealing resin composition>

[0155] (Average particle size and maximum particle size of inorganic filler)

[0156] In an image of a thin sheet sample of the sealing resin composition taken with a scanning electron microscope, the major diameters (μm) of 100 randomly selected inorganic fillers were measured and the arithmetic average was taken as the average particle size. The maximum value of the 100 major diameters (μm) was taken as the maximum particle size.

[0157] (Spiral Flow)

[0158] The sealing resin composition was molded using a spiral flow measurement mold in accordance with EMMI-1-66 under the conditions of a mold temperature of 180° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance (cm) was determined.

[0159] (Narrow path filling)

[0160] Prepare Figure 1 and Figure 2 The test chip of the form shown in the figure. That is, three chips 3 (10 mm in length × 10 mm in width × 250 μm in thickness) obtained by dicing silicon wafers are arranged on a substrate 1 (50 mm in length × 250 mm in width × 0.2 mm in thickness) via a die attach tape 6 (1.0 mm in width, 40 μm in thickness) and pressure-bonded at 200°C for 10 seconds.

[0161] Next, the sealing resin composition was loaded 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, and then post-cured at 180° C. for 5 hours. The molding dimensions were set on the substrate 1 to be 50 mm in length×250 mm in width×0.5 mm in thickness.

[0162] The 1 mm distance between the chip 3 and the substrate 1 is measured from the surface opposite to the device mounting surface. 2 Calculate the total area of ​​the above gaps.

[0163] (Relative dielectric constant and dielectric loss tangent)

[0164] The sealing resin composition was placed in a vacuum manual press, molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 600 seconds, and cured at 180°C for 6 hours to obtain a plate-shaped cured product (12.5 mm in length, 25 mm in width, and 0.2 mm in thickness). The plate-shaped cured product was used as a test piece, and a dielectric constant measuring device (Agilent Technologies, trade name "Network Analyzer N5227A") was used to measure the relative dielectric constant and dielectric loss tangent at about 60 GHz at a temperature of 25±3°C.

[0165] (Water absorption)

[0166] The plate-shaped solidified product immediately after production was placed in a pressure cooker cooking test apparatus at 121° C. / 2.1 atmospheres, taken out after 24 hours, and the rate of increase (%) relative to the mass immediately before placement was determined.

[0167] [Table 1]

[0168]

[0169] With respect to all documents, patent applications, and technical standards described in this specification, each document, patent application, and technical standard is introduced by reference to the same extent as if it were specifically and separately described, and is introduced by reference into this specification to that extent.

[0170] Description of Reference Numerals

[0171] 1: Substrate

[0172] 3: Chip

[0173] 6: Chip mounting tape.

Claims

1. Application of sealing resin composition in narrow path filling, The sealing resin composition contains epoxy resin, curing agent and inorganic filler. The curing agent comprises an active ester compound, The average particle size of the inorganic filler material is greater than 5 μm and less than 10 μm. The maximum particle size of the inorganic filler material is less than 20 μm, The narrow path refers to a gap between a supporting member and an element or between adjacent elements, wherein at least one of the height and the width is 100 μm or less.

2. The use according to claim 1, in, The active ester compound includes at least one selected from the group consisting of a phenol ester compound, a thiophenol ester compound, an N-hydroxylamine ester compound, and an ester of a heterocyclic hydroxyl compound.

3. The use according to claim 1, in, The active ester compound contains at least one selected from an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing an aromatic structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac.

4. The use according to claim 1, which is used in mold bottom filling.

5. The use according to any one of claims 1 to 4, in, The mass increase rate of the cured product of the sealing resin composition determined by a pressure cooker cooking test under conditions of 121° C., 2.1 atmospheres, and 24 hours, that is, the water absorption rate of the cured product is 0% to 0.35%.

6. An electronic component device comprising a supporting member, an element arranged on the supporting member, and a cured product of a sealing resin composition filling a narrow path around the element, The sealing resin composition contains epoxy resin, curing agent and inorganic filler. The curing agent comprises an active ester compound, The average particle size of the inorganic filler material is greater than 5 μm and less than 10 μm. The maximum particle size of the inorganic filler material is less than 20 μm, The narrow path refers to a gap between a supporting member and an element or between adjacent elements, wherein at least one of the height and the width is 100 μm or less.

7. A method for manufacturing an electronic component device, comprising the steps of arranging an element on a supporting member and filling a narrow path around the element with a sealing resin composition, The sealing resin composition contains epoxy resin, curing agent and inorganic filler. The curing agent comprises an active ester compound, The average particle size of the inorganic filler material is greater than 5 μm and less than 10 μm. The maximum particle size of the inorganic filler material is less than 20 μm, The narrow path refers to a gap between a supporting member and an element or between adjacent elements, wherein at least one of the height and the width is 100 μm or less.

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