TWI816889B - Resin composition for sealing, electronic component device and method of manufacturing electronic component device - Google Patents

Abstract

A resin composition for sealing for use in narrow-path filling, comprising an epoxy resin, a curing agent and an inorganic filler, wherein the curing agent includes an active ester compound, and an average particle diameter of the inorganic filler is less than 10 µm.

Description

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

The present invention relates to a sealing resin composition, an electronic component device, and a manufacturing method of the electronic component device.

The amount of transmission loss caused by thermal conversion of radio waves transmitted for communication in a dielectric material is expressed as the product of the frequency, the square root of the relative permittivity, and the dielectric tangent. That is, the transmission signal easily becomes hot 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 material of the communication member.

For example, Patent Documents 1 to 2 disclose a thermosetting resin composition containing an active ester resin as a curing agent for epoxy resin, which can suppress the dielectric tangent of the cured product to a low level.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2012-246367

[Patent Document 2] Japanese Patent Application Laid-Open No. 2014-114352

In the field of information communication, as the number of channels increases and the amount of information transmitted increases, the frequency of radio waves is developing. Research on fifth-generation mobile communication systems is currently being carried out all over the world, and several candidates for the frequency bands to be used can be listed in the range of approximately 30GHz to 70Ghz. In the future, the mainstream of wireless communications will be communications in such a high frequency band, so materials for communication components are required to have lower dielectric tangents.

In addition, as semiconductor devices become smaller, thinner, or more functional, the bump pitch or the distance between elements becomes narrower, and a sealing resin composition excellent in narrow path filling properties is required.

The embodiments of the present disclosure are based on the above circumstances.

An object of the present disclosure is to provide a sealing resin composition that is excellent in narrow path filling properties and has a low dielectric tangent of the cured product, an electronic component device sealed using the sealing resin composition, and an electronic component device sealed using the electronic component device. manufacturing method.

Specific methods for solving the above problems include the following aspects.

[1] A sealing resin composition for narrow road filling, the sealing resin composition contains an epoxy resin, a hardener and an inorganic filler, the hardener contains an active ester compound, and the inorganic filler The average particle size is less than 10 μm.

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

[3] The sealing resin composition as described in [1] or [2] is used as a base filler for molds.

[4] An electronic component device including: a support member, a component arranged on the support member, and a seal according to any one of [1] to [3] that fills a narrow path around the component A hardened product of a resin composition.

[5] A method of manufacturing an electronic component device, including the steps of arranging a component on a supporting member, and filling the component with the sealing resin composition according to any one of [1] to [3]. The steps around the narrow road.

According to the present disclosure, there are provided a sealing resin composition that is excellent in narrow path filling properties and has a low dielectric tangent of the cured product, an electronic component device sealed using the sealing resin composition, and an electronic component device sealed using the electronic component device. Manufacturing methods.

1:Substrate

3:Mold

6:Mold adhesive tape

FIG. 1 is a plan view (partial perspective view) illustrating a test wafer used in Examples.

FIG. 2 is a cross-sectional view illustrating a test wafer used in Examples.

In this disclosure, the term "step" includes steps other than steps that are independent from other steps, even if they cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved.

In this disclosure, in the numerical range represented by "~", the numerical values recorded before and after "~" are respectively regarded as the minimum value and the maximum value.

Among the numerical ranges described in stages in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced by the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical range described in this disclosure, the upper limit value or the lower limit value of the numerical range can also be replaced with the value shown in the embodiment.

In this disclosure, each component may also include multiple equivalent substances. When there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the multiple substances present in the composition.

In this disclosure, a plurality of particles corresponding to each component may also be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle diameter of each component refers to a value for a mixture of the plurality of types of particles present in the composition unless otherwise specified.

In this disclosure, when an embodiment is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. In addition, the sizes of members in each figure are conceptual sizes, and the relative size relationship between members is not limited to this.

<Sealing resin composition>

The sealing resin composition of the present disclosure is a sealing resin composition for narrow path filling, and contains an epoxy resin, a hardener and an inorganic filler. The hardener contains an active ester compound, and the average particle size of the inorganic filler is not Full 10μm.

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

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

Examples of the embodiment include a sealing resin composition for mold underfill (MUF) that seals a component placed on a support member and fills a gap between the support member and the component; system level Sealing resin compositions for system in a package (SiP), etc.

The active ester compound of the present disclosure refers to a compound that has one or more ester groups that react with an epoxy group in one molecule and has a hardening effect on the epoxy resin.

Previously, phenol hardeners, amine hardeners, etc. were generally used as hardeners for epoxy resins. However, secondary hydroxyl groups are generated during the reaction between epoxy resins and phenol hardeners or amine hardeners. In contrast, in the reaction between the epoxy resin and the active ester compound, an ester group is generated in place of the secondary hydroxyl group. Since the ester group has lower polarity than the secondary hydroxyl group, the sealing resin composition of the present disclosure can be compared with a sealing resin composition containing only a hardener that generates a secondary hydroxyl group as a hardener. Electric tangent suppression is low.

Furthermore, since the average particle diameter of the inorganic filler contained in the sealing resin composition of the present disclosure is less than 10 μm, it is excellent in narrow path filling properties. This is presumably because when the melt of the sealing resin composition flows through the narrow passage, the inorganic filler is less likely to block the narrow passage.

The lower limit of the average particle size of the inorganic filler in the sealing resin composition of the present disclosure is not particularly limited. For example, from the viewpoint of suppressing aggregation of inorganic fillers, the thickness is preferably 3 μm or more.

(epoxy resin)

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

Specific examples of the epoxy resin include phenol compounds selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and α-naphthol and β-naphthalene. At least one phenolic compound in the group consisting of naphthol compounds such as phenol and dihydroxynaphthalene is condensed or co-condensed with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde and the like under an acidic catalyst to obtain a novolak resin and Novolak-type epoxy resin (phenol novolac-type epoxy resin, o-cresol novolac-type epoxy resin, etc.) obtained by epoxidation of the novolak resin; the phenolic compound is mixed with benzaldehyde, salicylaldehyde A triphenylmethane-type epoxy resin obtained by condensing or co-condensing aromatic aldehyde compounds under an acidic catalyst to obtain a triphenylmethane-type phenol resin and epoxidizing the triphenylmethane-type phenol resin; A copolymerized epoxy resin obtained by co-condensing the phenolic compound, naphthol compound and aldehyde compound under an acidic catalyst to obtain a novolac resin and epoxidizing the novolac resin; as bisphenol A, bisphenol F, etc. Diphenylmethane-type epoxy resin as a diglycidyl ether; Diphenyl-type epoxy resin as a diglycidyl ether of alkyl-substituted or unsubstituted biphenol; Diphenylmethane-type epoxy resin as a stilbene-based phenol compound stilbene type epoxy resin; sulfur atom-containing epoxy resin as diglycidyl ether of bisphenol S, etc.; as butylene glycol, polyethylene glycol, polyethylene glycol, etc. Epoxy resins that are glycidyl ethers of alcohols such as propylene glycol; glycidyl ester type epoxy resins that are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; aniline Glycidylamine type epoxy resin obtained by replacing the active hydrogen bonded to the nitrogen atom with a glycidyl group such as diaminodiphenylmethane, isocycyanuric acid, etc.; combining dicyclopentadiene with a phenolic compound Dicyclopentadiene-type epoxy resin obtained by epoxidation of co-condensation resin; diepoxidized vinylcyclohexene and 3,4-epoxycyclohexylmethyl obtained by epoxidation of olefin bonds in the molecule -3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxan alicyclic epoxy resins such as alkane; p-xylene modified epoxy resin which is the glycidyl ether of p-xylene modified phenol resin; m-xylene modified epoxy resin which is the glycidyl ether of m-xylene modified phenol resin Oxygen resin; Terpene-modified epoxy resin as glycidyl ether of terpene-modified phenol resin; Dicyclopentadiene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin as glycidyl ether of cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified epoxy resin as glycidyl ether of polycyclic aromatic ring-modified phenol resin; as naphthalene-containing Naphthalene-type epoxy resin of glycidyl ether of cyclic phenol resin; halogenated phenol novolak-type epoxy resin; hydroquinone-type epoxy resin; trimethylolpropane-type epoxy resin; use peracetic acid and other peracids to Linear aliphatic epoxy resins obtained by oxidizing olefin bonds; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin, etc. Furthermore, epoxy resins such as epoxides of acrylic resins can also be cited. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.

The epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 100g/eq to 1000g/eq is preferred, and 150g/eq to 500g/eq is more preferred.

The epoxy equivalent of the epoxy resin is a value measured by a method based on Japanese Industrial Standards (JIS) K 7236:2009.

When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, the temperature is preferably 40°C to 180°C, and from the viewpoint of workability during preparation of the sealing resin composition, the temperature is more preferably 50°C to 130°C.

The melting point or softening point of the epoxy resin is a value measured by a method based on differential scanning calorimetry (DSC) or JIS K 7234:1986 (ball and ball method).

From the viewpoint of strength, fluidity, heat resistance, formability, etc., the content rate of the epoxy resin in the sealing resin composition is preferably 0.5 mass% to 50 mass%, more preferably 2 mass% to 30 mass% %.

(hardener)

The sealing resin composition of the present disclosure contains at least an active ester compound as a hardener. The sealing resin composition of the present disclosure may contain a hardener other than the active ester compound.

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

In addition, the polar groups in the cured product increase the water absorbency of the cured product. By using an active ester compound as a curing agent, the polar group concentration of the cured product can be suppressed, and the water absorbency of the cured product can be suppressed. Furthermore, by suppressing the water absorption of the cured material, that is, suppressing the content of H ₂ O which is a polar molecule, the dielectric tangent of the cured material can be suppressed to a lower level. The water absorption rate of the hardened material is preferably 0% to 0.35%, more preferably 0% to 0.30%, and further preferably 0% to 0.25%. Here, the water absorption rate of the cured material is the mass increase rate determined by the pressure cooking (PRESSURE COOKER) test (121° C., 2.1 atmospheric pressure, 24 hours).

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

Examples of active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxylamine ester compounds, esterified products of heterocyclic hydroxy compounds, and the like.

Examples of the active ester compound include an ester compound obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. An ester compound containing an aliphatic compound as a polycondensation component tends to have excellent compatibility with an epoxy resin because it has an aliphatic chain. An ester compound containing an aromatic compound as a polycondensation component tends to have excellent heat resistance because it has an aromatic ring.

Specific examples of the active ester compound include aromatic esters obtained by the condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups. Among them, aromatic compounds in which 2 to 4 hydrogen atoms of aromatic rings such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with carboxyl groups are preferred. Family carboxylic acid component, a monohydric phenol in which one hydrogen atom of the aromatic ring is replaced by a hydroxyl group, and two of the aromatic ring Aromatic esters obtained by the condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups are a mixture of polyphenols in which ~4 hydrogen atoms are substituted with hydroxyl groups as raw materials. That is, an aromatic ester having 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 is preferred.

Specific examples of the active ester compound include phenol resins having a molecular structure in which a phenol compound is knotted via aliphatic cyclic hydrocarbon groups and aromatic dicarboxylic acids described in Japanese Patent Application Laid-Open No. 2012-246367. Or an active ester resin with a structure obtained by reacting its halide with an aromatic monohydroxy compound. As the active ester resin, a compound represented by the following structural formula (1) is preferred.

In the structural formula (1), R ¹ is an alkyl group with 1 to 4 carbon atoms, and , Y is a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted by an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n represents the average number of repeats and is 0.25 to 1.5.

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 the third butyl group.

[Chemicalization 2]

[Chemical 3]

Other specific examples of the active ester compound include a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3) described in Japanese Patent Application Laid-Open No. 2014-114352.

In the structural formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms, and Z is selected from benzyl group and naphthyl group. The ester forming structural part (z1) or At least one of the hydrogen atoms (z2) and Z is an ester-forming structural part (z1).

In the structural formula (3), R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms, and Z is selected from benzyl group and naphthyl group. The ester forming structural part (z1) or At least one of the hydrogen atoms (z2) and Z is an ester-forming structural part (z1).

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

[Chemistry 5]

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

[Chemical 6]

As the active ester compound, a commercially available product can also be used. As commercially available active ester compounds, active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Co., Ltd. ); examples of active ester compounds containing aromatic structures include “EXB9416-70BK”, “EXB-8”, and “EXB-9425” (manufactured by DIC Co., Ltd.); examples of active ester compounds containing an acetate of phenol novolac include Examples include "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); examples of active ester compounds containing benzyl compounds of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd. Co., Ltd.), etc.

One type of active ester compound may be used alone, or two or more types may be used in combination.

The ester group equivalent of the active ester compound is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 150g/eq~400g/eq is preferred, 170g/eq~300g/eq is more preferred, and 200g/eq~ is still more preferred. 250g/eq.

The ester group equivalent of the active ester compound is a value measured according to the method of JIS K 0070:1992.

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

From the viewpoint of suppressing less 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.

The hardener may also contain hardeners other than active ester compounds. In this case, the type of other hardener is not particularly limited and can be selected based on the required characteristics of the sealing resin composition. Examples of other hardeners include phenol hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, and block isocyanate hardeners.

Specific examples of the phenol hardener include: resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol and other polyphenol compounds; Free phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenolic compounds and α-naphthol, β-naphthol, di- Novolak type phenolic resin obtained by condensation or co-condensation of at least one phenolic compound in the group of naphthol compounds such as hydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde and other aldehyde compounds under an acidic catalyst; Aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin synthesized from phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc.; p-xylene modification Phenol resin, m-xylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene type phenol resin synthesized by copolymerization of the phenolic compound and dicyclopentadiene And dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; making the phenolic compound be aromatic with benzaldehyde, salicylaldehyde, etc. triphenylmethane-type phenol resin obtained by condensation or co-condensation of aldehyde compounds under an acidic catalyst; phenol resin obtained by copolymerizing two or more of these. One type of these phenol hardeners may be used alone, or two or more types may be used in combination.

The functional group equivalents of other hardeners (hydroxyl equivalents in the case of phenol hardeners) are not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 70g/eq to 1000g/eq is preferred, and 80g/eq to 500g/eq is more preferred.

The functional group equivalent of other curing agents (hydroxyl equivalent in the case of a phenol curing agent) is a value measured by a method based on JIS K 0070:1992.

When the hardener is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, 40°C to 180°C is preferred. From the viewpoint of workability during production of the sealing resin composition, 50°C to 130°C is more preferred.

The melting point or softening point of the hardener is a value measured in the same manner as the melting point or softening point of the epoxy resin.

The equivalent ratio of epoxy resin to all hardeners (active ester compounds and other hardeners), that is, the ratio of the number of functional groups in the hardener to the number of functional groups in the epoxy resin (number of functional groups in the hardener/in epoxy resin The number of functional groups) is not particularly limited. From the viewpoint of suppressing each unreacted component as little as possible, it is preferably set to the range of 0.5 to 2.0, and more preferably set to the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

From the viewpoint of suppressing the dielectric tangent of the cured material to be low, the content rate 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. More preferably, it is 90 mass % or more.

From the viewpoint of keeping the dielectric tangent of the cured product 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 mass % or more. , more preferably 80 mass% or more, further preferably 85 mass% or more.

(hardening accelerator)

The sealing resin composition may also contain a hardening accelerator. The type of hardening accelerator is not particularly limited and can be selected according to the type of epoxy resin or hardener, the required characteristics of the sealing resin composition, and the like.

Examples of hardening accelerators include: 1,5-diazabicyclo[4.3.0]nonene-5 (1,5-Diazabicyclo[4.3.0]nonene-5, DBN), 1,8-Diazabicyclo[5.4.0]undecene-7(1,8-Diazabicyclo[5.4.0]undecene- 7, DBU) and other diazabicyclic olefins, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other cyclic amidine compounds; the ring Derivatives of cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or derivatives thereof; and addition of 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 - Compounds with intramolecular polarization formed from quinone compounds such as dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds with π bonds such as diazophenylmethane; DBU Cyclic amidinium compounds such as tetraphenyl boron salt, DBN tetraphenyl boron salt, 2-ethyl-4-methylimidazole tetraphenyl boron salt, N-methylmorpholine tetraphenyl boron salt and so on, and Compounds formed by adding isocyanates; 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, tris(dimethylaminomethyl)phenol; the tertiary amine Derivatives of compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-n-hexylammonium benzoate, tetrapropylammonium hydroxide, etc.; triphenylphosphine , diphenyl(p-toluene)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 Tertiary phosphines such as phenyl) phosphine, trialkyl phosphine, dialkyl aryl phosphine, alkyl diaryl phosphine; phosphine compounds such as complexes of the tertiary phosphine and organic boron; the tertiary phosphine phosphine or the Phosphine compounds and 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, diazo Compounds with intramolecular polarization formed by the addition of compounds with π bonds such as phenylmethane; in making the tertiary phosphine or the 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-naphthol , 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and other halogenated phenol compounds are obtained through the dehydrohalogenation step and have intramolecular polarization. Compounds; tetraphenylphosphonium and other tetrasubstituted phosphoniums, tetra-p-toluene borate and other tetrasubstituted phosphoniums and tetrasubstituted borates that do not have a phenyl group bonded to the boron atom; salts of tetraphenylphosphonium and phenolic compounds; tetraalkanes Salts of partial hydrolysates of phosphonium and aromatic carboxylic acid anhydrides, etc.

When the sealing resin composition contains a hardening accelerator, the amount is preferably 0.1 to 30 parts by mass, more preferably 1,000 parts by mass relative to 100 parts by mass of the resin component (total amount of epoxy resin and hardener) Parts by mass ~15 parts by mass. If the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency for good curing in a short time. When the amount of the curing accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, a good molded article in which the curing speed is not too fast tends to be obtained.

(Inorganic filler material)

The average particle size of the inorganic filler contained in the sealing resin composition of the present disclosure is not Full 10μm. From the viewpoint of improving narrow path filling properties, the average particle diameter of the inorganic filler is less than 10 μm, and preferably less than 9 μm. From the viewpoint of suppressing aggregation of inorganic fillers, the average particle diameter of the inorganic filler is preferably 3 μm or more, more preferably 5 μm or more.

From the viewpoint of further improving narrow path filling properties, the sealing resin composition of the present disclosure preferably contains an inorganic filler whose maximum particle diameter is less than 30 μm, more preferably less than 25 μm, and still more preferably less than 20 μm. .

The average particle size of the inorganic filler was determined by measuring the long diameter of 100 randomly selected inorganic fillers from an image of a sheet sample of the sealing resin composition or its hardened product taken with a scanning electron microscope. The value obtained by arithmetic mean. The maximum particle diameter of the inorganic filler is the maximum value among the 100 long diameters.

The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystallized silica, glass, alumina, talc, clay, and mica. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc composite hydroxides, zinc borate, and the like.

Among the inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of the form of the inorganic filler include powder, particles obtained by spheroidizing the powder, and fibers.

The content rate of the inorganic filler contained in the sealing resin composition is not Special restrictions. From the viewpoint of fluidity and strength, it is preferably 30 volume % to 90 volume % of the entire sealing resin composition, more preferably 35 volume % to 80 volume %, and still more preferably 40 volume % to 70 volume %. If the content of the inorganic filler is 30 volume % or more of the entire sealing resin composition, the properties of the cured product, such as thermal expansion coefficient, thermal conductivity, and elastic modulus, tend to further improve. When the content rate of the inorganic filler is 90 volume % or less of the entire sealing resin composition, an increase in the viscosity of the sealing resin composition is suppressed, the fluidity is further improved, and the moldability tends to become better.

[Various additives]

In addition to the above-mentioned components, the sealing resin composition may also contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, and colorants exemplified below. In addition to the additives exemplified below, the sealing resin composition may optionally contain various additives well known in the art.

(coupling agent)

The sealing resin composition may also contain a coupling agent. From the viewpoint of improving the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureasilane, vinylsilane, and disilazane, titanium-based compounds, and aluminum chelate compounds. Well-known coupling agents such as aluminum/zirconium-based compounds.

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass based on 100 parts by mass of the inorganic filler. If the amount of coupling agent is relative to the inorganic filler When the content is 0.05 parts by mass or more per 100 parts by mass, the adhesiveness 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 formability of the package tends to be further improved.

(ion exchanger)

The sealing resin composition may contain an ion exchanger. From the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed element, the sealing resin composition preferably contains an ion exchanger. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. One type of ion exchanger may be used alone, or two or more types of ion exchangers may be used in combination. Among them, hydrotalcite represented by the following general formula (A) is preferred.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _X/2. mH ₂ O. ． ． ． ． ． ₍ A)

(0<X≦0.5, m is a positive number)

When the sealing resin composition contains an ion exchanger, its content is not particularly limited as long as it is a sufficient amount to capture halogen ion plasma. For example, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass relative to 100 parts by mass of the resin component (total amount of epoxy resin and hardener).

(release agent)

From the viewpoint of obtaining good releasability from the mold during molding, the sealing resin composition may contain a release agent. The release agent is not particularly limited, and conventionally known ones can be used. Specific examples include: carnauba wax, higher fatty acids such as octacarboxylic acid and stearic acid, ester waxes such as higher fatty acid metal salts, ester waxes such as octacarboxylic acid esters, oxygen Chemical polyethylene, non-oxidized polyethylene and other polyolefin waxes. One type of release agent may be used alone, or two or more types may be used in combination.

When the sealing resin composition contains a release agent, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1, based on 100 parts by mass of the resin component (total amount of epoxy resin and hardener) Parts by mass ~5 parts by mass. When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, sufficient release properties tend to be obtained. If it is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardant)

The sealing resin composition may also contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic compounds or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, and the like. One type of flame retardant may be used alone, or two or more types may be used in combination.

When the sealing resin composition contains a flame retardant, the amount is not particularly limited as long as it is a sufficient amount 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 (total amount of epoxy resin and hardener).

(colorant)

The sealing resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead, and iron oxide. The content of the colorant can be appropriately selected depending on the purpose and the like. A colorant may be used individually by 1 type, and may be used in combination of 2 or more types.

(Preparation method of sealing resin composition)

The method of preparing the sealing resin composition is not particularly limited. As a general method, the following method can be mentioned: after fully mixing the predetermined compounding amount of components with a mixer etc., melt-kneading with a grinding roll, an extruder etc., cooling and grinding|pulverizing. More specifically, for example, the following method can be cited: uniformly stirring and mixing a predetermined amount of the above ingredients, kneading and cooling using a kneader, roller, extruder, etc. that has been preheated to 70°C to 140°C, and then cooling. Crush.

The sealing resin composition is preferably solid at normal temperature and pressure (for example, 25° C. and atmospheric pressure). The shape of the sealing resin composition when it is solid is not particularly limited, and examples include powder, granular, flake, and the like. From the viewpoint of operability, when the sealing resin composition is in a sheet form, the size and quality are preferably those that match the molding conditions of the package.

<Electronic component device>

An electronic component device as one embodiment of the present disclosure includes a support member, a component arranged on the support member, and a cured product of the sealing resin composition of the present disclosure filling a narrow path around the component.

An electronic component device as one embodiment of the present disclosure has a narrow path filled with the sealing resin composition of the present disclosure. Examples of the narrow path include a gap between a supporting member and an element, a gap between adjacent elements, and the like. The electronic component device which is an embodiment of the present disclosure can also seal a part or the entirety other than the narrow path using the sealing resin composition of the present disclosure.

Examples of electronic component devices include sealing resin compositions such as It is obtained by sealing the lower component part, which is a component (semiconductor wafer, transistor, diode) mounted on a support member such as a lead frame, wired conveyor tape, wiring board, glass, silicon wafer, organic substrate, etc. Active components such as bodies and thyristors, passive components such as capacitors, resistors, coils, etc.).

More specifically, they can be listed: Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (Small Outline Package, SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have a component that is fixed to a lead frame and the terminal portion and lead portion of components such as bonding pads are connected by wire bonding, bumps, etc., and then a sealing resin composition is used and A structure that is sealed by transfer molding, etc.; Tape Carrier Package (TCP), which has a structure that uses a sealing resin composition to seal components connected to the carrier tape with bumps; Chip On Board (Chip On Board) , COB) modules, hybrid ICs, polycrystalline modules, etc., which have a method of sealing components on wiring formed on a supporting member by wire bonding, flip chip bonding, solder, etc., using a sealing resin composition. Structure; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), which has a support member with terminals for wiring board connection formed on the back surface After the component is mounted and connected to the wiring formed on the supporting member by bumps or wire bonding, the sealing resin composition is used to seal the component. The structure of sealing components; SiP (system in a package), etc., which seals multiple components in a package.

<Manufacturing method of electronic component device>

The method of manufacturing an electronic component device of the present disclosure includes the steps of arranging a component on a supporting member and filling a narrow path around the component with the sealing resin composition of the present disclosure.

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

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

Examples of methods for filling narrow passages around components using the sealing resin composition of the present disclosure include low-pressure transfer molding, injection molding, and compression molding. Among these, the low-pressure transfer molding method is usually used.

[Example]

The embodiments will be described in detail below using examples, but the scope of the embodiments is not limited to these examples.

<Preparation of sealing resin composition>

The components shown below were mixed in the mixing ratios shown in Table 1 to prepare sealing resin compositions of Examples and Comparative Examples. The sealing resin composition is at room temperature It is solid under normal pressure.

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

． Epoxy resin 2: Triphenylmethane type epoxy resin, epoxy equivalent 167g/eq (Mitsubishi Chemical Co., Ltd., product name "1032H60")

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

． Active ester compound 1: DIC Co., Ltd., product name "EXB-8"

． Active ester compound 2: DIC Co., Ltd., product name "EXB-9425"

． Phenol hardener 1: phenol aralkyl resin, hydroxyl equivalent weight 175g/eq (Meiwa Chemical Co., Ltd., product name "MEH7800SS")

． Hardening accelerator 1: triphenylphosphine/1,4-benzoquinone adduct

． Hardening accelerator 2: imidazole compound (Shikoku Chemical Industry Co., Ltd., brand name "Curezol 2E4MZ")

． Filler 1: Molten silica (DENKA Co., Ltd., product name "FB-310MDC")

． Filler 2: Fused silica (Micron Corporation, product name "ST7010-2")

． Filler 3: Fused silica (Admatechs, product name "SO-25R")

． Filler 4: Molten silica (DENKA Co., Ltd., product name "FB-9454FC")

． Filler 5: Fused silica (Micron Corporation, product name "ST7010-3")

． Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., brand name "KBM-573")

． Coupling agent 2: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., brand name "KBM-803")

． Release agent: octacosate wax (Japanese Clariant Co., Ltd., product name "HW-E")

． Colorant: Carbon black (Mitsubishi Chemical Co., Ltd., product name "MA600")

<Performance evaluation of sealing resin compositions>

(Average particle size and maximum particle size of inorganic filler)

In an image of a sheet sample of the sealing resin composition taken with a scanning electron microscope, the major diameter (μm) of 100 randomly selected inorganic fillers was measured, and the arithmetic mean was calculated as the average particle diameter. In addition, the maximum value among the 100 major diameters (μm) was defined as the maximum particle diameter.

(Swirl)

Using a swirl flow measurement mold in compliance with EMMI-1-66, the sealing resin composition was molded under the conditions of mold temperature 180° C., molding pressure 6.9 MPa, and hardening time 90 seconds, and the flow distance (cm) was determined.

(narrow road filling)

A test wafer having the form shown in Figures 1 and 2 is prepared. That is, on the substrate 1 (length 50mm×width 250mm×thickness 0.2mm), die attach tape (Die Attach) is interposed. tape) 6 (width 1.0 mm, thickness 40 μm), three molds 3 (length 10 mm × width 10 mm × thickness 250 μm) with cut silicon wafers were placed, and pressure bonding was performed at 200°C for 10 seconds.

Next, the sealing resin composition was put into a transfer molding machine, molded under the conditions of a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 150 seconds, and cured at 180°C for 5 hours. The molding dimensions on the substrate 1 are 50 mm in length × 250 mm in width × 0.5 mm in thickness.

The area of the visible gap of 1 mm ² or more between the mold 3 and the substrate 1 was measured from the surface opposite to the component mounting surface, and the total area was calculated.

(relative permittivity and dielectric tangent)

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

(water absorption rate)

The plate-shaped hardened product immediately after production was put into a pressure cooker test device at 121° C./2.1 air pressure, and was taken out after 24 hours, and the increase rate (%) relative to the mass immediately before being put in was determined.

All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if each individual document, patent application, or technical specification was specifically and individually stated to be incorporated by reference. middle.

The disclosure of International Application No. PCT/JP2018/036100 filed on September 27, 2018 is incorporated into this specification in its entirety by reference.

Claims (7)

A sealing resin composition used for narrow road filling, and is solid powder, granular or flake-like at 25°C and atmospheric pressure. The sealing resin composition contains epoxy resin, hardener and inorganic filler , the hardener contains an active ester compound, the equivalent ratio (ester group/epoxy group) of the epoxy resin to the active ester compound is 0.9 to 1.1, and the average particle size of the inorganic filler is less than 10 μm. The sealing resin composition according to claim 1, wherein the maximum particle size of the inorganic filler is less than 20 μm. The sealing resin composition according to claim 1 or 2, wherein the content of the active ester compound is 80% by mass or more relative to the total amount of the hardener. The sealing resin composition described in Item 1 or Item 2 of the patent application is used as a primer for casting molds. An electronic component device including: a support member, a component arranged on the support member, and a seal as described in any one of items 1 to 4 of the patent application for filling a narrow path around the component A hardened product of a resin composition. A method of manufacturing an electronic component device, including the steps of arranging components on a support member, and The step of filling the narrow path around the component with the sealing resin composition described in any one of claims 1 to 4. In the method for manufacturing an electronic component device described in claim 6, the filling is performed by a low-pressure transfer molding method, an injection molding method, or a compression molding method.