TW202024168A - 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 manufacturing method of electronic component device

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

With the increase in density and output of electronic communication equipment, the heat generation of semiconductor devices tends to increase. Therefore, in order to improve the heat dissipation properties of materials for sealing semiconductor devices, improvement in thermal conductivity has been studied. For example, Patent Document 1 describes an epoxy resin composition for sealing in which 60% by volume or more of the inorganic filler is alumina in order to improve thermal conductivity.

On the other hand, the amount of transmission loss caused by thermal conversion of radio waves transmitted for communication in the dielectric is expressed in the form of the product of frequency, the square root of the relative permittivity, and the dielectric tangent. That is, the transmission signal tends to become heat in proportion to the frequency. Therefore, in order to suppress transmission loss, the higher the frequency band, the lower the dielectric properties required for the material of the communication member.

In the field of information communication, with the increase in the number of channels and the increase in the amount of information transmitted, the high frequency of radio waves is developing. Currently, research on the 5th generation mobile communication system is being carried out all over the world. As for the candidates for the frequency band to be used, several types in the range of approximately 30 GHz to 70 Ghz can be cited. In the future, the mainstream of wireless communication is communication in such a high frequency band. Therefore, the material of the communication member is required to further improve the dielectric properties. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-31460

[The problem to be solved by the invention] When alumina is used as the inorganic filler of the resin composition for sealing, there is a possibility that the thermal conductivity is high and the heat dissipation is improved, on the other hand, the relative dielectric constant increases and the transmission loss increases.

In view of the above-mentioned circumstances, the subject of the present disclosure is to provide a resin composition for sealing that is excellent in the balance of heat dissipation and dielectric properties of the cured product, an electronic component device sealed with the resin composition for sealing, and an electronic component device sealed with the electronic component device Manufacturing method of electronic component device. [Means to solve the problem]

Specific methods to solve the above-mentioned problems include the following aspects. <1> A resin composition for sealing, containing an epoxy resin, a hardener containing an active ester compound, and an inorganic filler containing alumina. <2> The resin composition for sealing according to <1>, wherein the proportion of alumina in the entire inorganic filler is 50% by mass or more. <3> An electronic component device, comprising: a support member, an element arranged on the support member, and a cured product of the sealing resin composition according to <1> or <2> that seals the element. <4> A method of manufacturing an electronic component device, including a step of arranging a component on a supporting member, and a step of sealing the component with the sealing resin composition as described in <1> or <2>. [Effects of the invention]

According to the present disclosure, there is provided a resin composition for sealing that is excellent in the balance of heat dissipation and dielectric properties of a cured product, an electronic component device sealed with the resin composition for sealing, and manufacturing of an electronic component device sealed with the electronic component device method.

In the present disclosure, in the term "step", in addition to a step independent of other steps, even if it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved, the step is also included. In the present disclosure, the numerical values described before and after "～" in the numerical range indicated by "～" are used as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. In the present disclosure, each component may also include multiple equivalent substances. When there are multiple types of substances corresponding to each component in the composition, unless otherwise specified, the content or content of each component means the total content or content of the multiple types of substances present in the composition. In the present disclosure, multiple particles corresponding to each component may also be included. When there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle size of each component refers to a value with respect to a mixture of the multiple types of particles present in the composition.

＜Resin composition for sealing＞ The sealing resin composition of the present disclosure is a sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and an inorganic filler containing alumina.

The results of research by the inventors have shown that the cured product obtained by curing the sealing resin composition having the above-mentioned configuration is compared with the cured product of the previous sealing resin composition using epoxy resin and curing agent , The cured product has an excellent balance of heat dissipation and dielectric properties. The reason is not necessarily clear, but it is considered as follows.

First, the resin composition for sealing of the present disclosure contains alumina as an inorganic filler. This achieves high thermal conductivity compared with the case where the sealing resin composition contains other inorganic fillers such as silica. Furthermore, the resin composition for sealing of this indication contains an active ester compound as a hardening agent. Phenolic hardeners and amine hardeners commonly used as hardeners for epoxy resins are equivalent to generating secondary hydroxyl groups in the reaction with epoxy resins. In contrast, in the reaction between the epoxy resin and the active ester compound, an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a 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 curing agent that generates a secondary hydroxyl group as a curing agent. The electric tangent is suppressed low. As a result, by using alumina as the inorganic filler, even if the relative dielectric constant increases, the increase in transmission loss can be suppressed.

(Epoxy) The type of epoxy resin contained in the resin composition for sealing of the present disclosure is not particularly limited. Specific examples of epoxy resins include phenolic compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and α-naphthol and β-naphthalene. At least one phenolic compound in the group consisting of naphthol compounds such as phenol and dihydroxy naphthalene is condensed or co-condensed with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolac resin and The novolak type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.) obtained by epoxidizing the novolak resin; combining the phenolic compound with benzaldehyde and salicylaldehyde And other aromatic aldehyde compounds are condensed or co-condensed under an acidic catalyst to obtain a triphenylmethane type phenol resin and the triphenylmethane type phenol resin is epoxidized to obtain a triphenylmethane type epoxy resin; The phenol compound and the naphthol compound and the aldehyde compound are co-condensed under an acid catalyst to obtain a novolak resin and the novolak resin is epoxidized to obtain a copolymer type epoxy resin; as bisphenol A, bisphenol F, etc. Diphenylmethane type epoxy resin of diglycidyl ether; Biphenyl type epoxy resin of diglycidyl ether of alkyl-substituted or unsubstituted biphenol; Diglycidyl ether of stilbene-based phenol compound Stilbene type epoxy resin; sulfur atom-containing epoxy resin as diglycidyl ether of bisphenol S; epoxy resin as glycidyl ether of alcohols such as butanediol, polyethylene glycol and polypropylene glycol Resins; glycidyl ester type epoxy resins that are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; aniline, diaminodiphenylmethane, isotri Glycidylamine type epoxy resin obtained by substituting glycidyl groups for active hydrogen bonded to nitrogen atoms such as polycyanic acid; bicyclic ring obtained by epoxidizing co-condensed resin of dicyclopentadiene and phenol compound Pentadiene type epoxy resin; diepoxy vinylcyclohexene obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy Acid ester, 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclo(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; as a pair Para-xylene-modified epoxy resin of glycidyl ether of xylene-modified phenol resin; meta-xylene-modified epoxy resin of glycidyl ether of meta-xylene-modified phenol resin; and terpene-modified phenol resin Terpene-modified epoxy resin of glycidyl ether; dicyclopentadiene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; glycidol as phenolic resin of cyclopentadiene-modified Cyclopentadiene-modified epoxy resin of ether; polycyclic aromatic ring-modified epoxy resin of glycidyl ether as polycyclic aromatic ring-modified phenol resin; naphthalene type of glycidyl ether as phenol resin containing naphthalene ring Epoxy resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic ring obtained by oxidizing olefin bonds with peracetic acid and other peracids Oxygen resin; aralkyl type ring obtained by epoxidizing aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin Oxygen resin, etc. Furthermore, epoxide of acrylic resin etc. can also be mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.

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, it is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq.

Let the epoxy equivalent of an epoxy resin be the value measured by the method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236:2009.

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

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

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

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

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

The resin composition for sealing of the present disclosure uses an active ester compound as a curing agent as described above, so that the dielectric tangent of the cured product can be suppressed to be low. In addition, the polar groups in the cured product increase the water absorption of the cured product. By using an active ester compound as the curing agent, the concentration of the polar group in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. Furthermore, by suppressing the water absorption of the cured product, that is, suppressing the content of H ₂ O as a polar molecule, the dielectric tangent of the cured product can be suppressed to be lower. The water absorption of the hardened product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and still more preferably 0% to 0.25%. Here, the water absorption rate of the cured product is the mass increase rate determined by the PRESSURE COOKER test (121°C, 2.1 air pressure, 24 hours).

As long as the active ester compound is a compound having one or more ester groups that react with an epoxy group in the molecule, its kind is not particularly limited.

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

As the active ester compound, for example, 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 is mentioned. An ester compound containing an aliphatic compound as a polycondensation component tends to have an aliphatic chain and therefore has excellent compatibility with epoxy resins. An ester compound containing an aromatic compound as a polycondensation component tends to be excellent in heat resistance by having an aromatic ring.

As a specific example of an active ester compound, the aromatic ester obtained by the condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group is mentioned. Among them, preferred are aromatic rings 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. Carboxylic acid component, a mixture of a monohydric phenol in which one hydrogen atom of the aromatic ring is substituted by a hydroxyl group, and a mixture of a polyphenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted by a hydroxyl group as a raw material and An aromatic ester obtained by the condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group. That is, it is preferably 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.

Specific examples of the active ester compound include phenol resins having a molecular structure in which a phenol compound is knotted through an aliphatic cyclic hydrocarbon group described in JP 2012-246367 A, and having an aromatic dicarboxylic acid Or the active ester resin of the structure obtained by reacting its halide and aromatic monohydroxy compound. The active ester resin is preferably a compound represented by the following structural formula (1).

[化1]

In the structural formula (1), R ¹ is an alkyl group having 1 to 4 carbons, and X is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring substituted by an alkyl group having 1 to 4 carbons, or a biphenyl group , 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 repetitions and is 0.25 to 1.5.

As specific examples of the compound represented by the structural formula (1), for example, the following exemplified compounds (1-1) to (1-10) can be cited. T-Bu in the structural formula is the tertiary butyl group.

[化2]

[化3]

As other specific examples of the active ester compound, the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) described in JP 2014-114352 A can be cited.

[化4]

In the structural formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, and Z is selected from the group consisting of benzyl and naphthyl An acyl group, a benzyl group or naphthyl group substituted by an alkyl group having 1 to 4 carbons, and an ester in the group consisting of an acyl group having 2 to 6 carbons form a structural site (z1) or At least one of the hydrogen atom (z2) and Z is an ester forming structure site (z1).

[化5]

In the structural formula (3), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, and Z is selected from the group consisting of benzyl and naphthyl An acyl group, a benzyl group or naphthyl group substituted by an alkyl group having 1 to 4 carbons, and an ester in the group consisting of an acyl group having 2 to 6 carbons form a structural site (z1) or At least one of the hydrogen atom (z2) and Z is an ester forming structure site (z1).

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

[化6]

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

[化7]

As the active ester compound, commercially available products 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.) ); Active ester compounds containing aromatic structures include "EXB9416-70BK", "EXB-8", and "EXB-9425" (manufactured by DIC Co., Ltd.); active ester compounds containing phenol novolac acetate can be Examples include "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); active ester compounds containing phenol novolac-based benzyl compounds include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).

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

The ester 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, it is preferably 150 g/eq to 400 g/eq, more preferably 170 g/eq to 300 g/eq, and still more preferably 200 g/eq～250 g/eq.

Let the ester equivalent of an active ester compound be the value measured by the method based on JISK 0070:1992.

From the viewpoint 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 still more preferably 0.97 the 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 still more preferably 1.03 or less.

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

Specific examples of the phenol hardener include polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; selected from phenol, cresol, diphenol Cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenolic compounds and α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds Novolac-type phenol resin obtained by condensation or co-condensation of at least one phenolic compound and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde in the composition group under an acidic catalyst; from the phenolic compound and dimethoxy Para-xylene, bis(methoxymethyl) biphenyl and other synthetic phenol aralkyl resins, naphthol aralkyl resins and other aralkyl phenol resins; para-xylene modified phenol resin, meta-xylene modified Phenol resin; melamine-modified phenol resin; terpene-modified phenol resin; dicyclopentadiene-type phenol resin and dicyclopentadiene-type synthesized by copolymerization of the phenolic compound and dicyclopentadiene Naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; making the phenolic compound and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in an acid catalyst Triphenylmethane type phenol resin obtained by condensation or co-condensation; phenol resin obtained by copolymerizing two or more of these. These phenol hardeners may be used alone or in combination of two or more.

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

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

In the case where the hardener is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably from 40°C to 180°C, and from the viewpoint of workability during the production of the resin composition for sealing, it is more preferably from 50°C to 130°C.

The melting point or softening point of the hardening agent 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 (the number of functional groups in the hardener/the number of functional groups in the epoxy resin) The number of functional groups) is not particularly limited. From the viewpoint of reducing the respective unreacted components, 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 to the range of 0.8 to 1.2.

From the viewpoint of suppressing the dielectric tangent of the cured product to a low level, the content of the active ester compound relative to the total mass of the active ester compound and other curing agents is preferably 80% by mass or more, more preferably 85% by mass or more, More preferably, it is 90% by mass or more.

From the viewpoint of suppressing the dielectric tangent of the cured product to a low level, 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 still more preferably 90% by mass or more.

(Hardening accelerator) The resin composition for sealing may contain a hardening accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin or curing agent, the 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[4.3.0]nonene-5, DBN Diazabicycloalkenes such as bicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU), 2-methylimidazole, 2-phenylimidazole, 2- Cyclic amidine compounds such as phenyl-4-methylimidazole and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or derivatives thereof; and These compounds add maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone , 2,3-Dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds , Diazophenylmethane and other compounds with π bond forming compounds with intramolecular polarization; DBU tetraphenylboron salt, DBN tetraphenylboron salt, 2-ethyl-4-methylimidazole Cyclic amidinium compounds such as tetraphenyl boron salt and tetraphenyl boron salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamine Tertiary amine compounds such as ethyl alcohol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethyl acetate Ammonium, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide and other ammonium salt compounds; triphenylphosphine, diphenyl(p-toluene)phosphine, tri(alkylphenyl)phosphine, tris(alkoxybenzene) Group) phosphine, tris (alkyl alkoxy phenyl) phosphine, tris (dialkyl phenyl) phosphine, tris (trialkyl phenyl) phosphine, tris (tetraalkyl phenyl) phosphine, tris (two Alkoxyphenyl) phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc. Phosphine compounds such as complexes of the tertiary phosphine and organoboron; Combining the tertiary phosphine or the phosphine compound with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-Naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2, Compounds with intramolecular polarization formed by addition of quinone compounds such as 3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds with π bonds such as diazophenylmethane ; To make 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- Bromine-4'- Halogenated phenol compounds such as hydroxybiphenyl are compounds with intramolecular polarization obtained after the step of dehydrohalogenation after the reaction; tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-p-toluene borate, etc. do not bond with boron atoms Phenyl tetra-substituted phosphonium and tetra-substituted borate; tetraphenyl phosphonium and phenol compounds, tetraalkyl phosphonium and aromatic carboxylic acid anhydride partial hydrolysate salt, etc.

When the sealing resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass relative to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent) Parts by mass ~ 15 parts by weight. If the amount of the hardening accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency to harden well in a short time. If the amount of the hardening accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, there is a tendency to obtain a good molded product with a hardening rate that is not too fast.

(Inorganic filler) The resin composition for sealing of this disclosure contains alumina as an inorganic filler. By including alumina, the thermal conductivity of the hardened product can be expected to increase. On the other hand, from the viewpoint of balance with other properties such as the coefficient of linear expansion and dielectric properties of the cured product, it is preferable to use alumina and an inorganic filler other than alumina in combination.

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

Among the inorganic fillers, from the viewpoint of reducing the coefficient of linear expansion, silicon dioxide such as molten silicon dioxide is preferred. The inorganic filler may be used alone or in combination of two or more. Examples of the form of the inorganic filler include powder, particles obtained by spheronizing powder, fibers, and the like.

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

The proportion of alumina in the inorganic filler contained in the resin composition for sealing is not particularly limited. From the viewpoint of increasing the thermal conductivity of the cured product, for example, it is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. From the viewpoint of balance with other properties of the cured product, for example, it is preferably 90% by mass or less.

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

[Various additives] The resin composition for sealing may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, and a coloring agent as exemplified below in addition to the above-mentioned components. In addition to the additives exemplified below, the resin composition for sealing may optionally contain various additives known in the technical field.

(Coupling agent) The resin composition for sealing may contain a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of coupling agents include epoxy silanes, mercapto silanes, amino silanes, alkyl silanes, urea silanes, vinyl silanes and other siloxane compounds, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds And other well-known coupling agents.

When the resin composition for sealing contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, 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 with respect 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 with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion Exchanger) The resin composition for sealing may contain an ion exchanger. From the viewpoint of improving the humidity resistance and high-temperature storage characteristics of an electronic component device provided with a sealed element, the resin composition for sealing preferably contains an ion exchanger. The ion exchanger is not particularly limited, and previously known ones can be used. Specifically, hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, and the like can be cited. One kind of ion exchanger may be used alone, or two or more kinds may be used in combination. 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 resin composition for sealing includes an ion exchanger, the content is not particularly limited as long as the content is a sufficient amount for capturing halogen ion plasma. For example, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent).

(Release agent) From the viewpoint of obtaining good releasability from the mold during molding, the resin composition for sealing may contain a mold release agent. The release agent is not particularly limited, and previously known ones can be used. Specific examples include: carnauba wax, higher fatty acids such as octadecanoic acid and stearic acid, higher fatty acid metal salts, ester waxes such as octadecanoate, and polyolefin-based waxes such as oxidized polyethylene and non-oxidized polyethylene Wax etc. One type of release agent may be used alone, or two or more types may be used in combination.

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

(Flame retardant) The resin composition for sealing may contain a flame retardant. The flame retardant is not particularly limited, and previously known ones can be used. Specifically, an organic compound or an inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, etc. can be mentioned. One kind of flame retardant may be used alone, or two or more kinds may be used in combination.

In the case where the resin composition for sealing contains a flame retardant, the amount is not particularly limited as long as the amount is sufficient to obtain the desired flame retardant effect. For example, with respect to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent), it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass.

(Colorant) The resin composition for sealing may contain a coloring agent. As the coloring agent, well-known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and iron oxide can be cited. The content of the coloring agent can be appropriately selected according to the purpose and the like. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more types.

(Preparation method of resin composition for sealing) The preparation method of the resin composition for sealing is not specifically limited. As a general method, the following method is mentioned: After fully mixing the components of a predetermined|prescribed compounding quantity by a mixer etc., melt-kneading by a grinding roll, an extruder, etc., it cools and crushes. More specifically, for example, a method of uniformly stirring and mixing a predetermined amount of the components, kneading and cooling using a kneader, roll, extruder, etc. heated to 70°C to 140°C, Shattered.

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

＜Electronic component device＞ An electronic component device as an embodiment of the present disclosure includes an element and a cured product of the sealing resin composition of the present disclosure that seals the element.

Examples of electronic component devices include those obtained by sealing the following component parts with a resin composition for sealing, the component parts being lead frames, wired conveyor tapes, wiring boards, glass, silicon wafers, organic substrates, etc. It is obtained by mounting components (semiconductor wafers, transistors, diodes, gates and other active components, capacitors, resistors, coils and other passive components, etc.) on the supporting member. More specifically, it can include: 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 (Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have components that are fixed on a lead frame and connect the terminals and lead portions of the components such as bonding pads by wire bonding, bumps, etc., and then use a sealing resin composition and use A structure for sealing such as transfer molding; Tape Carrier Package (TCP), which has a structure in which components connected to the carrier tape by bumps are sealed by a resin composition for sealing; Chip On Board (Chip On Board) , COB) modules, hybrid ICs, polycrystalline modules, etc., which have a sealing resin composition for sealing components connected to wiring formed on a support member by wire bonding, flip-chip bonding, solder, etc. Structure: Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (Multi Chip Package, MCP), etc., which have the surface of a supporting member forming wiring board connection terminals on the back A structure in which the component is mounted on the top, and the component is connected to the wiring formed on the support member by bumps or wire bonding, and then the component is sealed with a sealing resin composition. In addition, a resin composition for sealing can also be preferably used in a printed wiring board.

＜Method of manufacturing electronic component device＞ The manufacturing method of the electronic component device of the present disclosure includes a step of arranging components on a supporting member, and a step of sealing the components with the sealing resin composition of the present disclosure.

The method for implementing each step is not particularly limited, and it can be performed by a general method. In addition, the types of support members and elements used in the manufacture of electronic component devices are not particularly limited, and support members and elements generally used in the manufacture of electronic component devices can be used.

As a method of sealing an element using the resin composition for sealing of this disclosure, a low-pressure transfer molding method, an injection molding method, a compression molding method, etc. can be mentioned. Among these, the low-pressure transfer molding method is usually used. [Example]

Hereinafter, the embodiments are described in detail with examples, but the scope of the embodiments is not limited to these examples.

＜Preparation of resin composition for sealing＞ The components shown below were mixed in the formulation (parts by mass) shown in Table 1 to prepare the sealing resin compositions of Examples and Comparative Examples.

·Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 275 g/eq (Nippon Kayaku Co., Ltd., product name "NC-3000") ·Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 192 g/eq (Mitsubishi Chemical Corporation, product name "YX-4000")

· Hardener 1: Biphenyl aralkyl phenol resin, hydroxyl equivalent 199 g/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-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503") ·Coupling agent 2: 3-mercaptopropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-803")

·Release agent: Octacoate wax (Clariant Co., Ltd., product name "HW-E") ·Coloring agent: carbon black (Mitsubishi Chemical Corporation, product name "MA600") ·Additive: Triphenyl phosphine 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 18 μm) ·Inorganic filler 2: Silica filler (DENKA Co., Ltd., product name "FB-9454", average particle size 19 μm) ·Inorganic filler 3: Alumina/silica = 9/1 mixture (DENKA Co., Ltd., product name "DAB-10FC", average particle size 10 μm)

＜Performance evaluation of resin composition for sealing＞ (Swirl) Using a mold for swirl flow measurement based on EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance (cm) was determined.

(Gel time) Place 0.5 g of the sealing resin composition on a hot plate heated at 175°C, and use a jig to spread the sample evenly into a circle of 2.0 cm to 2.5 cm at a rotation speed of 20 to 25 revolutions/min. shape. After the sample is placed on the hot plate, the time it takes for the sample to disappear 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 a sealed composition, a vacuum manual press-forming machine was used to produce a test piece for thermal conductivity evaluation under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 250 kPa, and a curing time of 600 seconds (10 mm × 10 mm in length) 10 mm width × 0.8 mm thickness). Then, the thermal diffusivity in the thickness direction of the molded test piece was measured. The thermal diffusivity was measured by the laser flash method (device: LFA467 nanoflash, manufactured by NETZSCH). Pulsed light irradiation was performed under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247 V. The measurement is carried out at an ambient temperature of 25°C ± 1°C. In addition, the density of the test piece was measured using an electronic hydrometer (AUX220, Shimadzu Corporation). The specific heat is the theoretical specific heat of the sealing composition calculated based on the literature value of the specific heat of each material and the blending ratio. Then, using formula (1), the thermal diffusivity is multiplied by the specific heat and density to obtain the thermal conductivity value. λ=α×Cp×ρ Formula (1) (In Formula (1), λ represents the thermal conductivity (W/(m·K)), α represents the thermal diffusivity (m ² /s), and Cp represents the specific heat (J/ (Kg·K)), ρ means density (d: kg/m ³ ))

(Relative dielectric constant and dielectric tangent) The sealing resin composition is put 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. The resin composition is cured at 175°C for 6 hours to obtain a rod-shaped cured product (vertical 0.8 mm, width 0.6 mm, thickness 90 mm). The cured product was used as a test piece, and a cavity resonator (Kanto Electronics Application Development Co., Ltd., "CP561") and a network analyzer (Keysight Technologies, "PNA E8364B") were used to measure the temperature of 25±1 Relative permittivity and permittivity tangent at 20 GHz at ℃.

[Table 1] Comparative example 1 Comparative example 2 Comparative example 3 Example 1 Epoxy 1 75 75 - - Epoxy 2 25 25 100 100 Hardener 1 80.3 - 104 - Hardener 2 - 84.4 - 109 Hardening accelerator 1 2 4 2.5 5 Coupling agent 1 5 5 10 10 Coupling agent 2 0.15 0.15 0.15 0.15 Release agent 1 1 1 1 Colorant 2.7 2.7 2.7 2.7 additive - - 10 10 Inorganic filler 1 1326 1366 - - Inorganic filler 2 - - 317 327 Inorganic filler 3 - - 2020 2083 total 1520.85 1,566.95 2571.05 2,651.55 Inorganic filler amount (vol%) 78 78 78 78 Liquidity [inch] 47.1 56.5 41.9 57.1 Gel time [sec] 60 60 76 52 Thermal conductivity (W/(m·℃) 1.03 0.94 3.01 2.82 Relative permittivity Dk (20 GHz) 3.26 3.29 6.19 5.85 Dielectric Tangent Df (20 GHz) 0.0080 0.0044 0.0074 0.0047 Transmission loss (√Dk×Df) 0.015 0.0080 0.019 0.011

As shown in Table 1, the sealing resin composition of Example 1 and Comparative Example 3 that uses alumina as the inorganic filler is more effective than that of Comparative Example 1 and Comparative Example 2 that do not use alumina as the inorganic filler. High thermal conductivity. On the other hand, the relative permittivity of Example 1 and Comparative Example 3 was higher than that of Comparative Example 1 and Comparative Example 2. However, Example 1 using the active ester compound as the hardening agent has a lower dielectric tangent than Comparative Example 3 using the phenol resin as the hardening agent, so the increase in transmission loss is suppressed, resulting in a balance between heat dissipation and dielectric properties Excellent. In addition, in Example 1 and Comparative Example 2, by using an active ester with a lower viscosity than phenol resin as a curing agent, the fluidity was improved compared with Comparative Example 1 and Comparative Example 3 in which phenol resin was used as a curing agent. In Example 1 in which alumina was used as the inorganic filler, the fluidity improvement effect was greater than in Comparative Example 3 in which alumina was not used in combination as the inorganic filler. Furthermore, in Example 1, compared with Comparative Examples 1 to 3, the gel time was shorter. It is thought that alumina generally causes a delay in the curing reaction, but since the reactivity of the active ester compound and the epoxy resin is higher than that of the phenol resin and the epoxy resin, the curing property is improved.

no

Claims (4)

A resin composition for sealing contains an epoxy resin, a hardener containing an active ester compound, and an inorganic filler containing alumina. The resin composition for sealing as described in claim 1, wherein the proportion of alumina in the entire inorganic filler is 50% by mass or more. An electronic component device, including: Support components, Elements arranged on the supporting member, and The cured product of the sealing resin composition described in the first or second patent application for sealing the element. A manufacturing method of an electronic component device includes: Steps for arranging components on the supporting member, and The step of sealing the element with the sealing resin composition as described in item 1 or item 2 of the scope of patent application.