TWI854997B - Resin composition for sealing, electronic component device and method of manufacturing electronic component device - Google Patents

Abstract

A resin composition for sealing, comprising an epoxy resin, a curing agent including an active ester compound, and an inorganic filler including alumina.

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 method for manufacturing the electronic component device.

With the high density and high output of electronic communication equipment, the heat generation of semiconductor devices tends to increase. Therefore, in order to improve the heat dissipation of materials used to seal semiconductor devices, research is being conducted on improving thermal conductivity. For example, Patent Document 1 describes a sealing epoxy resin composition in which more than 60 volume % of the inorganic filler is aluminum oxide in order to improve thermal conductivity.

On the other hand, the transmission loss caused by heat conversion of radio waves transmitted for communication in the dielectric is expressed as the product of frequency, the square root of the relative dielectric constant, and the dielectric tangent. That is, the transmission signal tends to be converted into heat in proportion to the frequency, so in order to suppress transmission loss, the higher the frequency band, the lower the dielectric properties required of the material of the communication component.

In the field of information communication, with the increase in the number of channels and the amount of information transmitted, the frequency of radio waves is developing. Research on the fifth-generation mobile communication system is currently being conducted around the world, and several frequency bands in the range of about 30 GHz to 70 GHz can be listed as candidates. In the future, the mainstream of wireless communication will be communication at such a high frequency band, so the dielectric properties of the materials of communication components are required to be further improved.

[Prior art literature]

[Patent Literature]

[Patent document 1] Japanese Patent Publication No. 2014-31460

When alumina is used as an inorganic filler in a sealing resin composition, there is a concern that the thermal conductivity is high and the heat dissipation is improved, but on the other hand, the relative dielectric constant increases and the transmission loss increases.

In view of the above situation, the present disclosure aims to provide a sealing resin composition with an excellent balance between heat dissipation and dielectric properties of the cured product, an electronic component device sealed using the sealing resin composition, and a method for manufacturing an electronic component device sealed using the electronic component device.

The specific methods used to solve the above-mentioned problem include the following aspects.

<1> A sealing resin composition comprising: an epoxy resin, a hardener containing an active ester compound, and an inorganic filler containing aluminum oxide.

<2> The sealing resin composition as described in <1>, wherein the proportion of aluminum oxide in the entire inorganic filler is 50% by mass or more.

<3> An electronic component device comprising: a supporting member, a component disposed on the supporting member, and a cured product of the sealing resin composition described in <1> or <2> for sealing the component.

<4> A method for manufacturing an electronic component device, comprising: a step of arranging a component on a supporting member, and a step of sealing the component using a sealing resin composition as described in <1> or <2>.

According to the present disclosure, a sealing resin composition having an excellent balance between heat dissipation and dielectric properties of a cured product, an electronic component device sealed using the sealing resin composition, and a method for manufacturing an electronic component device sealed using the electronic component device are provided.

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

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

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

In this disclosure, each component may also include multiple equivalent substances. When there are multiple substances equivalent 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 the present disclosure, multiple types of particles corresponding to each component may also be included. When multiple types of particles corresponding to each component exist in a composition, unless otherwise specified, the particle size of each component refers to the value of the mixture of the multiple types of particles present in the composition.

<Sealing resin composition>

The sealing resin composition disclosed herein is the following sealing resin composition, which contains: epoxy resin, a hardener containing an active ester compound, and an inorganic filler containing aluminum oxide.

The research results of the inventors and others show that the cured product obtained by curing the sealing resin composition having the above structure has a better balance between heat dissipation and dielectric properties than the cured product of the sealing resin composition using the previous epoxy resin and hardener. The reason may not be clear, but it is considered as follows.

First, the sealing resin composition disclosed herein contains alumina as an inorganic filler. This achieves a higher thermal conductivity than when the sealing resin composition contains other inorganic fillers such as silica.

Furthermore, the sealing resin composition disclosed herein contains an active ester compound as a hardener. Phenol hardeners, amine hardeners, etc., which are commonly used as hardeners for epoxy resins, produce secondary hydroxyl groups in the reaction with epoxy resins. In contrast, in the reaction between epoxy resin and active ester compounds, ester groups are produced instead of secondary hydroxyl groups. Since ester groups have lower polarity than secondary hydroxyl groups, the sealing resin composition disclosed herein can suppress the dielectric tangent of the hardened material to a lower level than the sealing resin composition containing only a hardener that produces secondary hydroxyl groups as a hardener. As a result, by using aluminum oxide as an inorganic filler, the increase in transmission loss can be suppressed even if the relative dielectric constant increases.

(Epoxy)

There is no particular limitation on the type of epoxy resin contained in the sealing resin composition disclosed herein.

As the epoxy resin, specifically, there can be cited: a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, o-catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. and epoxidizing the novolac resin to obtain a novolac-type epoxy resin (phenol novolac-type epoxy resin, o-cresol novolac-type epoxy resin, etc.); condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylic aldehyde under an acidic catalyst to obtain a triphenylmethane-type phenolic resin and epoxidizing the triphenylmethane-type phenolic resin to obtain a triphenylmethane-type phenolic resin; a copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound under an acidic catalyst; a diphenylmethane epoxy resin as a diglycidyl ether of bisphenol A, bisphenol F, etc.; a biphenyl type epoxy resin as a diglycidyl ether of an alkyl-substituted or unsubstituted diphenol; Epoxy resins; styrene-type epoxy resins as diglycidyl ethers of styrene-based phenol compounds; sulfur-containing epoxy resins as diglycidyl ethers of bisphenol S, etc.; epoxy resins as glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; condensed glyceryl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid. Glyceryl ester epoxy resin; Glycerylamine epoxy resin obtained by replacing the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with glycidyl groups; Dicyclopentadiene epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; Diethylene oxide epoxy resin obtained by epoxidizing the olefinic bond in the molecule alicyclic epoxy resins such as hexene, 3,4-epoxyepoxyhexylmethyl-3,4-epoxyepoxyhexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; p-xylene-modified epoxy resin as the glycidyl ether of p-xylene-modified phenol resin; m-xylene as the glycidyl ether of m-xylene-modified phenol resin Modified epoxy resin; terpene-modified epoxy resin as the glycidyl ether of terpene-modified phenolic resin; dicyclopentadiene-modified epoxy resin as the glycidyl ether of dicyclopentadiene-modified phenolic resin; cyclopentadiene-modified epoxy resin as the glycidyl ether of cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified epoxy resin as the glycidyl ether of polycyclic aromatic ring-modified phenolic resin; Naphthalene-type epoxy resins of glycidyl ethers of phenol resins containing naphthalene rings; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trihydroxymethylpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins, etc. Furthermore, epoxides of acrylic resins can also be cited as epoxy resins. These epoxy resins can be used alone or in combination of two or more.

There is no particular restriction on the epoxy equivalent (molecular weight/number of epoxy groups) of epoxy resin. From the perspective of balancing various properties such as formability, reflow resistance, and electrical reliability, it is preferably 100g/eq~1000g/eq, and more preferably 150g/eq~500g/eq.

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

When the epoxy resin is solid, there is no particular restriction on its softening point or melting point. From the perspective of formability and reflow resistance, it is preferably 40°C to 180°C, and from the perspective of operability during the preparation of the sealing resin composition, it is more preferably 50°C to 130°C.

The melting point or softening point of the epoxy resin is set to a value measured by differential scanning calorimetry (DSC) or the method according to JIS K 7234:1986 (global method).

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

(hardener)

The sealing resin composition disclosed herein contains at least an active ester compound as a hardener. The sealing resin composition disclosed herein may also contain a hardener other than an active ester compound.

The active ester compound disclosed herein refers to a compound having one or more ester groups that react with epoxy groups in one molecule and having the curing effect of epoxy resin.

As described above, the sealing resin composition disclosed herein can suppress the dielectric tangent of the cured product to a low level by using an active ester compound as a curing agent.

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 the polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. Moreover, by suppressing the water absorption of the cured product, that is, suppressing the content of _H2O as a polar molecule, the dielectric tangent of the cured product can be suppressed to a lower level. The water absorption rate 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 rate of the cured product is the mass increase rate obtained by the pressure cooker test (121°C, 2.1 atmospheres, 24 hours).

The type of active ester compound is not particularly limited if it is a compound having one or more ester groups that react with epoxy groups in the molecule.

As active ester compounds, there can be listed: phenol ester compounds, thiophenol ester compounds, N-hydroxylamine ester compounds, esters of heterocyclic hydroxyl compounds, etc.

As active ester compounds, for example, ester compounds obtained from at least one of aliphatic carboxylic acid and aromatic carboxylic acid and at least one of aliphatic hydroxyl compound and aromatic hydroxyl compound can be cited. Ester compounds using aliphatic compounds as condensation components tend to have excellent compatibility with epoxy resins due to their aliphatic chains. Ester compounds using aromatic compounds as condensation components tend to have excellent heat resistance due to their aromatic rings.

As specific examples of active ester compounds, aromatic esters obtained by condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups can be cited. Among them, aromatic carboxylic acid components obtained by replacing 2 to 4 hydrogen atoms of aromatic rings of benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfonic acid, etc. with carboxyl groups, monohydric phenols obtained by replacing 1 hydrogen atom of the aromatic ring with hydroxyl groups, and polyhydric phenols obtained by replacing 2 to 4 hydrogen atoms of the aromatic ring with hydroxyl groups are preferably used as raw materials and obtained by condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups. That is, aromatic esters having structural units derived from the aromatic carboxylic acid components, structural units derived from the monohydric phenols, and structural units derived from the polyhydric phenols are preferably used.

Specific examples of active ester compounds include phenolic resins having a molecular structure in which a phenol compound is linked to an aliphatic cyclic hydrocarbon group as described in Japanese Patent Publication No. 2012-246367, and active ester resins having a structure obtained by reacting an aromatic dicarboxylic acid or a halogenated product thereof with an aromatic monohydroxy compound. The active ester resin is preferably a compound represented by the following structural formula (1).

In the structural formula (1), ^R1 is an alkyl group having 1 to 4 carbon atoms, X is a benzene ring, a naphthyl ring, a benzene ring or a naphthyl ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, Y is a benzene ring, a naphthyl ring, or a benzene ring or a naphthyl ring substituted with an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n represents the average number of repetitions and is 0.25 to 1.5.

As specific examples of the compound represented by the structural formula (1), the following exemplary compounds (1-1) to (1-10) can be cited. t-Bu in the structural formula is a tert-butyl group.

[Chemistry 3]

As other specific examples of active ester compounds, there can be cited compounds represented by the following structural formula (2) and compounds represented by the following structural formula (3) described in Japanese Patent Laid-Open No. 2014-114352.

In the structural formula (2), ^R1 and ^R2 are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is an ester-forming structural site (z1) or a hydrogen atom (z2) selected from the group consisting of a benzoyl group, a naphthyl group, a benzoyl group or a naphthyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, and at least one of Z is an ester-forming structural site (z1).

In the structural formula (3), ^R1 and ^R2 are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is an ester-forming structural site (z1) or a hydrogen atom (z2) selected from the group consisting of a benzoyl group, a naphthyl group, a benzoyl group or a naphthyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, and at least one of Z is an ester-forming structural site (z1).

As specific examples of the compound represented by structural formula (2), the following exemplary compounds (2-1) to (2-6) can be cited.

[Chemistry 6]

As specific examples of the compound represented by structural formula (3), the following exemplary compounds (3-1) to (3-6) can be cited.

[Chemistry 7]

As the active ester compound, commercial products can also be used. As commercial products of active ester compounds, active ester compounds containing dicyclopentadiene-type diphenol structures include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation); active ester compounds containing aromatic structures include "EXB9416-70BK", "EXB-8", and "EXB-9425" (manufactured by DIC Corporation); active ester compounds containing acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), etc.

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

There is no particular restriction on the ester equivalent of the active ester compound. From the perspective of balancing various properties such as formability, reflow resistance, and electrical reliability, it is preferably 150g/eq~400g/eq, more preferably 170g/eq~300g/eq, and even more preferably 200g/eq~250g/eq.

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

From the perspective of suppressing the dielectric tangent of the cured product to a low level, 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.

From the perspective 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.

The hardener may also include other hardeners other than the active ester compound. In this case, the type of other hardener is not particularly limited and can be selected according to the required properties of the sealing resin composition. Examples of other hardeners include phenol hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, and blocked isocyanate hardeners.

As the phenol hardener, specifically, there can be listed: polyphenol compounds such as resorcinol, o-catechin, bisphenol A, bisphenol F, substituted or unsubstituted biphenols, etc.; novolac type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, o-catechin, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc. with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acid catalyst; Aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized by copolymerizing the above-mentioned phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylic aldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these, etc. These phenolic hardeners may be used alone or in combination of two or more.

There is no particular restriction on the functional group equivalent of other hardeners (hydroxyl equivalent in the case of phenolic hardeners). From the perspective of balancing various properties such as formability, reflow resistance, and electrical reliability, it is preferably 70g/eq~1000g/eq, and more preferably 80g/eq~500g/eq.

The functional group equivalent weight (hydroxyl group equivalent weight in the case of phenolic hardener) of other hardeners is set to the value measured by the method based on JIS K 0070:1992.

When the hardener is solid, there is no particular restriction on its softening point or melting point. From the perspective of formability and reflow resistance, it is preferably 40°C to 180°C, and from the perspective of operability during the manufacture of the sealing resin composition, it is more preferably 50°C to 130°C.

The melting point or softening point of the hardener is set to the value measured in the same way 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/number of functional groups in the epoxy resin) is not particularly limited. From the perspective of suppressing the number of unreacted components, it is preferably set to a range of 0.5 to 2.0, and more preferably set to a range of 0.6 to 1.3. From the perspective of formability and reflow resistance, it is further preferably set to a range of 0.8 to 1.2.

From the perspective of suppressing the dielectric 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 further preferably 90 mass % or more.

From the perspective of suppressing the dielectric 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 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by 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 based on the type of epoxy resin or hardener, the required properties of the sealing resin composition, etc.

As hardening accelerators, there are 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and other diazabicycloalkenes. Cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and phenolic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3 Compounds with intramolecular polarization formed by using quinone compounds such as dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having π bonds such as diazonium methane; cyclic amidinium compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, and tetraphenylborate of N-methylporphyrin; pyridine tertiary amine compounds such as anthracene, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the 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-toluene)phosphine, tri(alkylphenyl ... A tertiary phosphine such as tri(alkyl-oxyphenyl)phosphine, tri(alkyl-alkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc.; a phosphine compound such as a complex of the tertiary phosphine and an organic boron; a compound having intramolecular polarization formed by adding the tertiary phosphine or the phosphine compound to 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, a compound having a π bond such as diazonophenylmethane; 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 Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as 2-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl and then undergoing a dehalogenation step; tetrasubstituted phosphoniums such as tetraphenylphosphonium, tetra-p-toluene borate and tetrasubstituted phosphoniums and tetrasubstituted borates without a phenyl group bonded to a boron atom; salts of partial hydrolyzates of tetraphenylphosphonium and phenol compounds, and tetraalkylphosphonium and aromatic carboxylic acid anhydrides, etc.

When the sealing resin composition contains a hardening 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 hardening agent). If the amount of the hardening 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 hardening accelerator is 30 parts by mass or less relative to 100 parts by mass of the resin component, there is a tendency to obtain a good molded product with a hardening speed that is not too fast.

(Inorganic filler)

The sealing resin composition disclosed herein contains alumina as an inorganic filler. By containing alumina, it is expected that the thermal conductivity of the cured product will be improved. On the other hand, from the perspective of the balance with other properties of the cured product such as the linear expansion coefficient and dielectric properties, it is preferred to use alumina and an inorganic filler other than alumina in combination.

Specifically, inorganic fillers other than alumina include fused silica, crystalline silica, glass, talc, clay, mica, and other inorganic materials. Inorganic fillers with flame retardant effects may also be used. Inorganic fillers with flame retardant effects include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient. Inorganic fillers may be used alone or in combination of two or more. Examples of the form of inorganic fillers include powder, granules obtained by sphericalizing powder, and fibers.

When the inorganic filler is in particle form, its average particle size is not particularly limited. For example, the average particle size is preferably 0.2μm~100μm, and more preferably 0.5μm~50μm. If the average particle size is 0.2μm or more, the increase in viscosity of the sealing resin composition tends to be further suppressed. If the average particle size is 100μm or less, the filling property tends to be further improved. The average particle size of the inorganic filler is obtained as the volume average particle size (D50) by a laser scattering diffraction particle size distribution measuring device.

There is no particular restriction on the proportion of alumina in the inorganic filler contained in the sealing resin composition. From the perspective of improving the thermal conductivity of the cured product, it is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. From the perspective of balancing other properties of the cured product, it is preferably 90% by mass or less.

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 volume% to 90 volume% of the entire sealing resin composition, more preferably 35 volume% to 80 volume%, and even 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 thermal expansion coefficient, thermal conductivity, elastic modulus and other properties of the cured product tend to be further improved. If the content of the inorganic filler is 90 volume% or less of the entire sealing resin composition, the viscosity of the sealing resin composition tends to be suppressed, the fluidity is further improved, and the moldability becomes better.

[Various additives]

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

(Coupling agent)

The sealing resin composition may also 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 coupling agents, there can be listed: silane compounds such as epoxysilane, ethylsilane, aminosilane, alkylsilane, ureasilane, vinylsilane, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds, and other well-known coupling agents.

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 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, the adhesion to the frame tends 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, the formability of the package tends to be further improved.

(ion exchanger)

The sealing resin composition may also contain an ion exchanger. From the viewpoint of improving the moisture resistance and high temperature storage characteristics of the electronic component device having the sealed element, the sealing resin composition preferably contains an ion exchanger. There is no particular limitation on the ion exchanger, and previously known ones can be used. Specifically, hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth can be listed. 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.

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 (the total amount of epoxy resin and hardener).

(Release agent)

From the perspective of obtaining good mold release properties from the mold during molding, the sealing resin composition may also contain a mold release agent. There is no particular limitation on the mold release agent, and previously known ones can be used. Specifically, they include: carnauba wax, higher fatty acids such as octadecanoic acid and stearic acid, higher fatty acid metal salts, ester waxes such as octadecanoic acid esters, oxidized polyethylene, non-oxidized polyethylene and other polyolefin waxes, etc. The mold release agent may be used alone or in combination of two or more.

When the sealing resin composition contains a mold release agent, its amount 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 hardener). If the amount of the mold 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 mold release properties. If it is 10 parts by mass or less, there is a tendency to obtain better adhesion.

(Flame retardant)

The sealing resin composition may also contain a flame retardant. There is no particular limitation on the flame retardant, and previously known ones may be used. Specifically, organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. may be listed. The flame retardant may be used alone or in combination of two or more.

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 (the total amount of epoxy resin and hardener).

(Colorant)

The sealing resin composition may also contain a colorant. Examples of the colorant include carbon black, organic dyes, organic pigments, titanium oxide, red lead, iron oxide, and other known colorants. The content of the colorant may be appropriately selected according to the purpose, etc. The colorant may be used alone or in combination of two or more.

(Method for preparing sealing resin composition)

There is no particular restriction on the preparation method of the sealing resin composition. As a general method, the following method can be cited: after the prescribed amount of ingredients is fully mixed by a mixer, etc., melt-kneading is performed by a grinding roll, an extruder, etc., cooling and crushing is performed. More specifically, for example, the following method can be cited: the prescribed amount of the ingredients is uniformly stirred and mixed, and kneading is performed by a kneader, roll, extruder, etc. pre-heated to 70°C~140°C, cooling, and crushing.

The sealing resin composition is preferably solid at normal 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 it can be powder, granular, sheet, etc. From the perspective of operability, the size and quality of the sealing resin composition when it is in sheet form are preferably the size and quality that match the molding conditions of the package.

<Electronic parts and devices>

An electronic component device as an embodiment of the present disclosure includes: a component, and a cured product of the sealing resin composition of the present disclosure that seals the component.

As electronic component devices, there can be cited those obtained by sealing the following component parts using a sealing resin composition, wherein the component parts are obtained by mounting components (active components such as semiconductor chips, transistors, diodes, gates, etc., passive components such as capacitors, resistors, coils, etc.) on supporting members such as lead frames, wired conveying tapes, wiring boards, glass, silicon wafers, and organic substrates.

More specifically, they include: Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), 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 structure in which the component is fixed on a lead frame and the terminal and lead portions of the component such as bonding pads are connected by wire bonding, bumps, etc., and then sealed using a sealing resin composition and by transfer molding, etc.; Tape Carrier Package (TAPE Package (TCP), which has a structure of sealing components connected to the carrier with bumps using a sealing resin composition; Chip On Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which have a structure of sealing components connected to wiring formed on a supporting member by wire bonding, flip chip bonding, solder, etc. using a sealing resin composition; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which have a structure of mounting components on the surface of a supporting member with terminals for wiring board connection formed on the back, and connecting the components to the wiring formed on the supporting member by bumps or wire bonding, and then sealing the components with a sealing resin composition. In addition, the sealing resin composition can also be preferably used in printed wiring boards.

<Method for manufacturing electronic component device>

The manufacturing method of the electronic component device disclosed herein includes: a step of arranging the component on a supporting member, and a step of sealing the component using the sealing resin composition disclosed herein.

There is no particular restriction on the method of implementing each of the steps, and it can be carried out by a general method. In addition, there is no particular restriction on the types of supporting members and components used in the manufacture of electronic parts and devices, and supporting members and components commonly used in the manufacture of electronic parts and devices can be used.

As methods for sealing components using the sealing resin composition disclosed herein, low-pressure transfer molding, injection molding, compression molding, etc. can be cited. Among these, low-pressure transfer molding is generally used.

[Implementation example]

The following is a detailed description of the implementation method through examples, but the scope of the implementation method is not limited to these examples.

<Preparation of sealing resin composition>

The following components were mixed in the formulation (mass parts) shown in Table 1 to prepare the sealing resin composition of the embodiment and the comparative example.

． Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 275g/eq (Nippon Kayaku Co., Ltd., product name "NC-3000")

． Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 192g/eq (Mitsubishi Chemical Co., Ltd., product name "YX-4000")

． Hardener 1: Biphenyl aralkyl type phenol resin, hydroxyl equivalent 199g/eq (Air Water Co., Ltd., product name "HE200C-10")

． Hardener 2: Active ester compound (DIC Co., Ltd.)

． Hardening accelerator 1: p-benzoquinone adduct of triphenylphosphine

． Coupling agent 1: 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")

． Coupling agent 2: 3-butylpropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-803")

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

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

． Additive: Triphenylphosphine oxide (Beixing Chemical Industry Co., Ltd., product name "TP-50")

． Inorganic filler 1: Silica filler (DENKA Co., Ltd., product name "FB-9454FC", average particle size 18μm)

． Inorganic filler 2: Silica filler (DENKA Co., Ltd., product name "FB-9454", average particle size 19μm)

． Inorganic filler 3: Alumina/silicon dioxide = 9/1 mixture (DENKA Co., Ltd., product name "DAB-10FC", average particle size 10μm)

<Performance evaluation of sealing resin composition>

(Swirl)

Using a swirl flow measurement mold based on EMMI-1-66, the sealing resin composition was molded at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and the flow distance (cm) was calculated.

(Gel time)

0.5g of the sealing resin composition is placed on a hot plate heated to 175°C, and the sample is evenly spread out into a 2.0cm~2.5cm circle using a clamp at a rotation speed of 20 rpm~25 rpm. After placing the sample on the hot plate, the time it takes for the sample to lose its viscosity and become a gel state and peel off the hot plate is measured, and this is measured as the gel time (sec).

(Thermal conductivity)

Using the sealing composition, a test piece for thermal conductivity evaluation (10mm in length × 10mm in width × 0.8mm in thickness) was produced by a vacuum manual press molding machine at a mold temperature of 175°C to 180°C, a molding pressure of 250kPa, and a curing time of 600 seconds. Then, the heat diffusion rate in the thickness direction of the molded test piece was measured. The heat diffusion rate was measured using the laser flash method (device: LFA467 nanoflash, manufactured by NETZSCH). Pulse light irradiation was performed under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247V. The measurement was performed at an ambient temperature of 25°C ± 1°C. In addition, the density of the test piece was measured using an electronic densitometer (AUX220, Shimadzu Corporation). The specific heat was calculated based on the literature value of the specific heat of each material and the mixing ratio to obtain the theoretical specific heat of the sealing composition.

Then, using equation (1), the value of thermal conductivity is obtained by multiplying the heat diffusion rate by the specific heat and density.

λ=α×Cp×ρ Formula (1)

(In formula (1), λ represents thermal conductivity (W/(m·K)), α represents heat diffusion rate (m ² /s), Cp represents specific heat (J/(kg·K)), and ρ represents density (d: kg/m ³ ))

(Relative dielectric constant and dielectric tangent)

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 90 seconds. After curing at 175°C for 6 hours, a rod-shaped cured product (length 0.8 mm, width 0.6 mm, thickness 90 mm) was obtained. The cured product was used as a test piece, and the relative dielectric constant and dielectric tangent were measured at a temperature of 25±1°C and 20 GHz using a cavity resonator (Kanto Electronics Application Development Co., Ltd., "CP561") and a network analyzer (Keysight Technologies, "PNA E8364B").

As shown in Table 1, the sealing resin composition of Example 1 and Comparative Example 3 using alumina as an inorganic filler has a higher thermal conductivity than that of Comparative Example 1 and Comparative Example 2 not using alumina as an inorganic filler. On the other hand, the relative dielectric constant of Example 1 and Comparative Example 3 is increased compared with that of Comparative Example 1 and Comparative Example 2. However, Example 1 using an active ester compound as a hardener has a lower dielectric tangent than Comparative Example 3 using a phenolic resin as a hardener, thereby suppressing the increase in transmission loss, resulting in an excellent balance between heat dissipation and dielectric properties.

In addition, in Example 1 and Comparative Example 2, by using an active ester with a lower viscosity than the phenolic resin as a hardener, the fluidity is improved compared to Comparative Example 1 and Comparative Example 3 using the phenolic resin as a hardener, but the fluidity improvement effect of Example 1 using alumina as an inorganic filler is greater than that of Comparative Example 3 not using alumina as an inorganic filler.

Furthermore, in Example 1, the gelation time is shorter than in Comparative Examples 1 to 3. It is believed that aluminum oxide usually causes a delay in the curing reaction, but since the reactivity of the active ester compound with the epoxy resin is higher than that of the phenol resin with the epoxy resin, the curing property is improved.

Claims (3)

A sealing resin composition comprises: an epoxy resin, a hardener containing an active ester compound, and an inorganic filler containing alumina and silica, wherein the content of the inorganic filler is 40% to 90% by volume of the entire sealing resin composition, the proportion of alumina in the inorganic filler is 50% to 90% by mass, and the sealing resin composition is solid at 25°C and atmospheric pressure. An electronic component device includes: a supporting member, a component arranged on the supporting member, and a cured product of the sealing resin composition as described in Item 1 of the patent application scope for sealing the component. A method for manufacturing an electronic component device, comprising: a step of arranging a component on a supporting member, and a step of sealing the component using a sealing resin composition as described in item 1 of the patent application scope.