JP2020122071A - Sealing resin composition, electronic component device, and method for manufacturing same - Google Patents

Abstract

To provide a sealing resin composition with which a cured product has a low dielectric loss tangent.SOLUTION: A sealing resin composition includes an epoxy resin, a curing agent including an active ester compound, and a non-polar polymer.SELECTED DRAWING: None

Description

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

The amount of transmission loss caused by heat conversion of a radio wave transmitted for communication in a dielectric is expressed as a product of a frequency, a square root of a relative dielectric constant, and a dielectric loss tangent. That is, since the transmission signal is likely to change into heat in proportion to the frequency, the higher the frequency band, the lower the dielectric property of the material of the communication member is required to suppress the transmission loss.

For example, Patent Documents 1 and 2 disclose thermosetting resin compositions containing an active ester resin as a curing agent for epoxy resin, and it is said that the dielectric loss tangent of the cured product can be suppressed to be low.

JP 2012-246367 A JP, 2014-114352, A

In the field of information and communication, the frequency of radio waves is increasing with the increase in the number of channels and the amount of information transmitted. Currently, studies on the fifth-generation mobile communication system are being conducted worldwide, and some of the range of about 30 GHz to 70 GHz are mentioned as candidates for the frequency band to be used. In the future, since the mainstream of wireless communication will be communication in such a high frequency band, further low dielectric loss tangent is required for the material of the communication member.

The embodiments of the present disclosure have been made under the above circumstances.

The present disclosure provides a resin composition for encapsulation having a low dielectric loss tangent of a cured product, an electronic component device encapsulated using the same, and a method for manufacturing an electronic component device encapsulated using the same. And

Specific means for solving the problems include the following aspects.

<1> An encapsulating resin composition containing an epoxy resin, a curing agent containing an active ester compound, and a nonpolar polymer.
<2> The encapsulating resin composition according to <1>, wherein the non-polar polymer is thermoplastic.
<3> The nonpolar polymer contains an aromatic ring. The encapsulating resin composition according to <1> or <2>.
<4> The encapsulating resin composition according to any one of <1> to <3>, in which the nonpolar polymer contains a styrene polymer.
<5> Support member, element arranged on the support member, and cured product of the resin composition for sealing according to any one of <1> to <4>, which seals the element. An electronic component device comprising:
<6> An electronic component device including: a step of disposing an element on a support member; and a step of encapsulating the element with the encapsulating resin composition according to any one of <1> to <5>. Manufacturing method.

According to the present disclosure, there are provided a sealing resin composition having a low dielectric loss tangent of a cured product, an electronic component device sealed using the same, and a method for manufacturing an electronic component device sealed using the same. ..

In the present disclosure, the term “process” includes not only a process independent from other processes but also the process if the purpose of the process is achieved even when the process cannot be clearly distinguished from the other process. ..
In the present disclosure, the numerical range indicated by using "to" includes the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may include a plurality of types of applicable substances. When multiple types of substances corresponding to each component are present in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.

<Sealing resin composition>
The encapsulating resin composition of the present disclosure is an encapsulating resin composition containing an epoxy resin, a curing agent containing an active ester compound, and a nonpolar polymer.

As a result of the study by the present inventors, a cured product obtained by curing the encapsulating resin composition having the above-mentioned configuration is more than a cured product of a conventional encapsulating resin composition using an epoxy resin and a curing agent. It was found that the dielectric loss tangent was low. The reason is not clear, but it is considered as follows.

First, the sealing resin composition of the present disclosure contains an active ester compound as a curing agent. Phenol curing agents, amine curing agents and the like, which are generally used as curing agents for epoxy resins, generate secondary hydroxyl groups in the reaction with epoxy resins. On the other hand, 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 encapsulating resin composition of the present disclosure has, as compared with the encapsulating resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent, The dielectric loss tangent of the cured product can be kept low.

Furthermore, the sealing resin composition of the present disclosure contains a non-polar polymer. It is considered that this reduces the concentration of polar groups such as secondary hydroxyl groups in the cured product of the encapsulating resin composition, and can further suppress the dielectric loss tangent of the cured product.

(Non-polar polymer)
In the present disclosure, “non-polar polymer” means a polymer that does not have a polar group such as a hydroxyl group, an amino group, a carboxy group, a carbonyl group, and an isocyanuric group.
However, a polymer having only a polar group that is unintentionally included during production, storage, etc. is also regarded as a “nonpolar polymer”.

The type of non-polar polymer is not particularly limited. Specific examples of the non-polar polymer include indene-styrene-coumarone copolymers, styrene-based polymers containing styrene such as polystyrene as a polymerization component, polyphenyl ether polymers, polyolefins such as polyethylene and polypropylene, and fluorine such as polytetrafluoroethylene. Examples thereof include polymers and silicones. These non-polar polymers may be used alone or in combination of two or more.

Among the above non-polar polymers, from the viewpoint of thermoplasticity and workability, non-polar polymers containing an aromatic ring are preferable, styrene-based polymers (polymers containing structural units derived from styrene) are more preferable, and indene-styrene-coumarone copolymers are preferable. Polymers are more preferred.

The non-polar polymer may be thermoplastic or thermosetting, and can be selected according to desired properties of the encapsulating resin composition and the like. From the viewpoint of reducing the elasticity of the cured product of the encapsulating resin composition, it is preferably thermoplastic.

In some embodiments, the non-polar polymer may be a polymer of 3 or more monomers, a polymer of 5 or more monomers, and a polymer of 10 or more monomers. It may be a united body. In some embodiments, the non-polar polymer may be free of fatty acid-derived structures. In some embodiments, the non-polar polymer may be free of ester bonds.

The content of the nonpolar polymer in the encapsulating resin composition is 3 parts by mass to 50 parts by mass with respect to 100 parts by mass of the epoxy resin, from the viewpoint of the effect of reducing the concentration of the polar group and the balance with other components. The amount is preferably 10 parts by mass to 30 parts by weight, and more preferably.

(Epoxy resin)
The type of epoxy resin contained in the encapsulating resin composition of the present disclosure is not particularly limited.
Specific examples of the epoxy resin include at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolak type epoxy resin, which is obtained by epoxidizing a novolak resin obtained by condensing or co-condensing a certain phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. Epoxy resin, orthocresol novolak type epoxy resin, etc.); Epoxy triphenylmethane type phenol resin obtained by condensing or co-condensing the above phenolic compound and an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst Triphenylmethane type epoxy resin which is a epoxidized compound; Copolymer type epoxy resin which is an epoxidized novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; Bisphenol A, diphenyl methane type epoxy resin which is diglycidyl ether such as bisphenol F; biphenyl type epoxy resin which is diglycidyl ether of alkyl substituted or unsubstituted biphenol; stilbene type epoxy resin which is diglycidyl ether of stilbene type phenol compound; bisphenol Sulfur atom-containing epoxy resin which is diglycidyl ether such as S; Epoxy resin which is glycidyl ether of alcohol such as butanediol, polyethylene glycol, polypropylene glycol; Polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, tetrahydrophthalic acid Glycidyl ester type epoxy resin which is a glycidyl ester of glycidyl ester; glycidyl amine type epoxy resin in which active hydrogen bonded to nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid and the like is substituted with glycidyl group; dicyclopentadiene and phenol compound A dicyclopentadiene type epoxy resin obtained by epoxidizing a condensation resin; vinyl cyclohexene diepoxide obtained by epoxidizing an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5, Alicyclic epoxy resins such as 5-spiro(3,4-epoxy)cyclohexane-m-dioxane; para-xylylene-modified epoxy resins that are glycidyl ethers of para-xylylene-modified phenol resins; meta-xylylene-modified epoxy resins that are glycidyl ethers of meta-xylylene-modified phenol resins. A terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol resin; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring modified epoxy resin which is glycidyl ether of cyclic aromatic ring modified phenol resin; Naphthalene type epoxy resin which is glycidyl ether of naphthalene ring containing phenol resin; Halogenated phenol novolac type epoxy resin; Hydroquinone type epoxy resin; Trimethylolpropane -Type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; aralkyl-type epoxy resin obtained by epoxidizing aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. ; And the like. Further, an epoxy resin such as an epoxidized product of an acrylic resin can also be used. 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 various property balances such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq.

The epoxy equivalent of the epoxy resin is a value measured by a method according to JIS K 7236:2009.

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

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

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

(Curing agent)
The encapsulating resin composition of the present disclosure contains at least an active ester compound as a curing agent. The encapsulating resin composition of the present disclosure may include a curing agent other than the active ester compound.

The active ester compound in the present disclosure refers to a compound having one or more ester groups that react with an epoxy group in one molecule and having a curing action on an epoxy resin.

As described above, the encapsulating resin composition of the present disclosure can suppress the dielectric loss tangent of a cured product to a low level by using an active ester compound as a curing agent.
Further, when the polar group in the cured product enhances the water absorption of the cured product, the polar group concentration of the cured product can be suppressed by using an active ester compound as a curing agent, and the water absorption of the cured product can be suppressed. it can. Then, by suppressing the water absorption of the cured product, that is, by suppressing the content of H ₂ O which is a polar molecule, the dielectric loss tangent of the cured product can be further suppressed. The water absorption of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and further preferably 0% to 0.25%. Here, the water absorption rate of the cured product is a mass increase rate obtained by a pressure cooker test (121° C., 2.1 atmospheric pressure, 24 hours).

The type of the active ester compound is not particularly limited as long as it is a compound having at least one ester group that reacts with an epoxy group in the molecule.

Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified product of a heterocyclic hydroxy compound.

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

Specific examples of the active ester compound include aromatic esters obtained by condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenyl sulfonic acid are substituted with a carboxy group, and the hydrogen atom of the aromatic ring described above. Of the aromatic carboxylic acid and the phenolic hydroxyl group using as a raw material a mixture of a monohydric phenol in which one of the above is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 of the hydrogen atoms of the aromatic ring described above are substituted with a hydroxyl group. Aromatic esters obtained by condensation reaction are preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monohydric phenol, and a structural unit derived from the polyhydric phenol is preferable.

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

In structural formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms, X is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group. And Y is a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n represents the average of the number of repetitions. 25 to 1.5.

Specific examples of the compound represented by Structural Formula (1) include the following Exemplified Compounds (1-1) to (1-10). T-Bu in the structural formula is a tert-butyl group.

As another specific example of the active ester compound, a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3), which are described in JP-A-2014-114352. Can be mentioned.

In Structural Formula (2), R ¹ and R ² are each 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 a benzoyl group, a naphthoyl group, or a carbon atom. An benzoyl group or a naphthoyl group substituted with an alkyl group of 1 to 4 and an ester-forming structural site (z1) selected from the group consisting of an acyl group of 2 to 6 carbon atoms, or a hydrogen atom (z2), Z At least one of them is an ester-forming structural site (z1).

In structural formula (3), R ¹ and R ² are each 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 a benzoyl group, a naphthoyl group, or a carbon atom. An benzoyl group or a naphthoyl group substituted with an alkyl group of 1 to 4 and an ester-forming structural site (z1) selected from the group consisting of an acyl group of 2 to 6 carbon atoms, or a hydrogen atom (z2), Z At least one of them is an ester-forming structural site (z1).

Specific examples of the compound represented by Structural Formula (2) include the following Exemplified Compounds (2-1) to (2-6).

Specific examples of the compound represented by Structural Formula (3) include the following Exemplified Compounds (3-1) to (3-6).

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

The active ester compounds 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 various characteristics balance such as moldability, reflow resistance, and electrical reliability, 150 g/eq to 400 g/eq are preferable, 170 g/eq to 300 g/eq are more preferable, and 200 g/eq to 250 g/eq are preferable. More preferable.

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

The equivalent ratio of the epoxy resin and the active ester compound (ester group/epoxy group) is preferably 0.9 or more, more preferably 0.95 or more, and 0.97 or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. Is more preferable.
The equivalent ratio of the epoxy resin and the active ester compound (ester group/epoxy group) is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted content of the active ester compound. It is more preferably 03 or less.

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

Specific examples of the phenol curing agent include polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol. , At least one phenolic compound selected from the group consisting of phenol compounds such as aminophenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and an aldehyde compound such as formaldehyde, acetaldehyde and propionaldehyde as an acidic catalyst Novolak type phenol resin obtained by condensation or co-condensation under the following; aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin synthesized from the above phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. Paraxylylene-modified phenol resin, metaxylylene-modified phenol resin, melamine-modified phenol resin, terpene-modified phenol resin, dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol, which are synthesized by copolymerization from the above phenolic compound and dicyclopentadiene Resin: cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl type phenol resin; obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst. Triphenylmethane type phenolic resin obtained; a phenolic resin obtained by copolymerizing two or more of these, and the like. These phenol curing agents may be used alone or in combination of two or more.

The functional group equivalent of other curing agents (hydroxyl group equivalent in the case of a phenol curing agent) is not particularly limited. From the viewpoint of various characteristics balance such as moldability, 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.

Functional group equivalents of other curing agents (hydroxyl group equivalents in the case of phenol curing agents) are values measured by a method according to JIS K 0070:1992.

When the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability at the time of producing the encapsulating resin composition, it is more preferably 50°C to 130°C. ..

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

Equivalent ratio of the epoxy resin to all curing agents (active ester compounds and other curing agents), ie the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (the number of functional groups in the curing agent/the number of functional groups in the epoxy resin) The number of functional groups) is not particularly limited. From the viewpoint of suppressing the amount of each unreacted component, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

The content of the active ester compound with respect to the total mass of the active ester compound and the other curing agent is preferably 80% by mass or more, and more preferably 85% by mass or more from the viewpoint of suppressing the dielectric loss tangent of the cured product. It is preferably 90% by mass or more, and more preferably 90% by mass or more.

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 the other curing agent is preferably 80% by mass or more and 85% by mass from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. % Or more, and more preferably 90% by mass or more.

(Curing accelerator)
The encapsulating resin composition may include a curing accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin or curing agent, desired characteristics of the encapsulating resin composition, and the like.

Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5(DBN) and 1,8-diazabicyclo[5.4.0]undecene-7(DBU). Cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; Derivatives of the cyclic amidine compounds; Phenolic novolac salts of the cyclic amidine compounds or their derivatives; To 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; and diazophenylmethane, and other compounds having a π-bonded compound have an intramolecular polarization. Compound: Cyclic amidinium compound such as tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, tetraphenylborate salt of 2-ethyl-4-methylimidazole, tetraphenylborate salt of N-methylmorpholine, and isocyanate are added. Compounds: DBU isocyanate adduct, DBN isocyanate adduct, 2-ethyl-4-methylimidazole isocyanate adduct, N-methylmorpholine isocyanate adduct; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanol Tertiary amine compounds such as amine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, benzoin Ammonium salt compounds such as tetra-n-hexyl ammonium acid and tetrapropyl ammonium hydroxide; triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxy) Phenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phos Tertiary phosphines such as fin, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine and alkyldiarylphosphine; phosphine compounds such as complexes of the tertiary phosphine and organic borons; the tertiary phosphine or the phosphine Compounds and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1, A compound having an intramolecular polarization formed by adding a compound having a π bond, such as 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, and diazophenylmethane and the like. The tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodinated phenol, 3-iodinated Phenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4- Halogenated phenols such as bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl. After reacting the compound, a compound having an intramolecular polarization obtained through a step of dehydrohalogenation; a tetra-substituted phosphonium such as tetraphenylphosphonium or a phenyl group bonded to a boron atom such as tetra-p-tolylborate Examples include tetra-substituted phosphonium and tetra-substituted borate; salts of tetraphenylphosphonium with a phenol compound; salts of tetraalkylphosphonium with a partial hydrolyzate of an aromatic carboxylic acid anhydride.

When the encapsulating resin composition contains a curing accelerator, the amount thereof is preferably 0.1 parts by mass to 30 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). It is more preferably 1 part by mass to 15 parts by mass. When the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that the composition is cured well in a short time. If the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing speed will not be too fast, and a good molded article will tend to be obtained.

(Inorganic filler)
The encapsulating resin composition of the present disclosure may contain an inorganic filler. The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay, mica, boron nitride, and aluminum nitride. You may use the inorganic filler which has a flame retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, magnesium oxide, complex metal hydroxide such as complex hydroxide of magnesium and zinc, zinc borate and the like.

Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic fillers may be used alone or in combination of two or more. Examples of the form of the inorganic filler include non-powder, spherical beads, fibers and the like.

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

The content of the inorganic filler contained in the encapsulating resin composition is not particularly limited. From the viewpoint of fluidity and strength, 30% by volume to 90% by volume of the entire encapsulating resin composition is preferable, 35% by volume to 80% by volume is more preferable, and 40% by volume to 70% by volume. % Is more preferable. When the content of the inorganic filler is 30% by volume or more of the entire encapsulating resin composition, properties such as the thermal expansion coefficient, thermal conductivity and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire encapsulating resin composition, an increase in the viscosity of the encapsulating resin composition is suppressed, the fluidity is further improved, and the moldability is better. Tend to be.

[Various additives]
The encapsulating resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, and a colorant, which are exemplified below, in addition to the above components. The encapsulating resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.

(Coupling agent)
The sealing resin composition may include a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and other silane compounds, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds, and the like. ..

When the encapsulating resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably about 2.5 parts by mass. When 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 adhesiveness with the frame tends to be further improved. When 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 sealing resin composition may include an ion exchanger. The encapsulating resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and the high-temperature storage property of the electronic component device including the element to be encapsulated. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds, and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchangers may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

_{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 encapsulating resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to trap ions such as halogen ions. For example, it is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass 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)
The encapsulating resin composition may include a release agent from the viewpoint of obtaining good releasability from the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specific examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts and ester waxes such as montanic acid esters. The release agents may be used alone or in combination of two or more.

When the encapsulating resin composition contains a release agent, the amount thereof is preferably 0.01 parts by mass 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), More preferably, it is from 5 parts by mass to 5 parts by mass. When the amount of the releasing agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the releasing property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The encapsulating resin composition may include a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardants may be used alone or in combination of two or more.

When the encapsulating resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain a desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 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).

(Colorant)
The encapsulating resin composition may include a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. The colorants may be used alone or in combination of two or more.

(Method for preparing encapsulating resin composition)
The method for preparing the encapsulating resin composition is not particularly limited. As a general method, there can be mentioned a method in which predetermined components are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, cooled, and pulverized. More specifically, for example, a method of uniformly agitating and mixing predetermined amounts of the above-mentioned components, kneading with a kneader, roll, extruder or the like preheated to 70°C to 140°C, cooling, and pulverizing. Can be mentioned.

The encapsulating resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25° C. and atmospheric pressure). The shape of the encapsulating resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, and tablets. From the viewpoint of handleability, it is preferable that the size and weight of the encapsulating resin composition in the form of a tablet be such that it meets the molding conditions of the package.

<Electronic component device>
An electronic component device according to an embodiment of the present disclosure includes an element and a cured product of the encapsulating resin composition of the present disclosure, which encapsulates the element.

As an electronic component device, elements (semiconductor chips, transistors, diodes, thyristors, etc. , A passive element such as a coil) and an element portion obtained by mounting the element portion with a sealing resin composition.
More specifically, the element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding, bumps or the like, and then transfer molding or the like is performed using a sealing resin composition. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outlet OP Package), SOJ (Small Outlet Tray, Jap). General resin encapsulation type IC such as Outlook Package), TQFP (Thin Quad Flat Package), etc.; TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is encapsulated with an encapsulating resin composition. A COB (Chip On Board) module, a hybrid IC, and a multi-circuit having a structure in which an element connected to the wiring formed on the support member by wire bonding, flip chip bonding, solder, etc. is sealed with a sealing resin composition. Chip module or the like; an element is mounted on the surface of a supporting member having terminals for connecting a wiring board formed on the back surface, and after connecting the element and the wiring formed on the supporting member by bump or wire bonding, a resin composition for sealing Examples include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package), which have a structure in which an element is sealed with an object. Moreover, the resin composition for sealing can be used suitably also in a printed wiring board.

<Method for manufacturing electronic component device>
The method for manufacturing an electronic component device of the present disclosure includes a step of disposing an element on a support member, and a step of sealing the element with the sealing resin composition of the present disclosure.

The method for carrying out each of the above steps is not particularly limited, and a general method can be used. Further, the types of the supporting member and the element used for manufacturing the electronic component device are not particularly limited, and the supporting member and the element generally used for manufacturing the electronic component device can be used.

Examples of the method of encapsulating an element using the encapsulating resin composition of the present disclosure include a low pressure transfer molding method, an injection molding method, and a compression molding method. Among these, the low pressure transfer molding method is general.

Hereinafter, the above-described embodiments will be specifically described with reference to examples, but the scope of the above-described embodiments is not limited to these examples.

<Preparation of resin composition for sealing>
The components shown below were mixed at the compounding ratio shown in Table 1 to prepare encapsulating resin compositions of Examples and Comparative Examples.

Epoxy resin 1: biphenylene 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")

-Active ester compound: Active ester compound (DIC Corporation)

・Nonpolar polymer: Indene-styrene-coumarone copolymer (Nippon Chemical Co., Ltd.)

-Curing accelerator: triphenylphosphine/p-benzoquinone adduct

Filler: fused silica (Denka Corporation, volume average particle size 10 μm)

-Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")
-Coupling agent 1:3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
-Release agent: montanic acid ester wax (Clariant Japan KK, product name "HW-E")
・Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")

<Performance evaluation of sealing resin composition>
(Relative permittivity and loss tangent)
The encapsulating resin composition was charged into a transfer molding machine, molded under the conditions of a mold temperature of 175° C., a molding pressure of 2.5 MPa and a curing time of 600 seconds, and post-cured at 175° C. for 6 hours to obtain a plate-shaped cured product. (Length 12.5 mm, width 25 mm, thickness about 0.2 mm) was obtained. Using the plate-shaped cured product as a test piece, a relative dielectric constant and dielectric loss tangent at 60 GHz were measured at a temperature of 25±3° C. using a dielectric constant measuring device (Agilent, product name “Network Analyzer N5227A”).

(Hot hardness)
The sealing resin composition was charged 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 to obtain a disk-shaped molded product (diameter 40 mm, thickness 5 mm). Obtained. The Shore D hardness within 10 seconds after releasing the mold was measured using a Shore D hardness meter.

As shown in Table 1, the encapsulating resin composition of Example containing an active ester compound as a curing agent and containing a non-polar polymer was the same as that of Comparative Example containing an active ester compound as a curing agent but not containing a non-polar polymer. The value of the dielectric loss tangent of the cured product was lower than that of the encapsulating resin composition.

Claims (6)

A sealing resin composition containing an epoxy resin, a curing agent containing an active ester compound, and a nonpolar polymer. The encapsulating resin composition according to claim 1, wherein the non-polar polymer is thermoplastic. The encapsulating resin composition according to claim 1 or 2, wherein the non-polar polymer contains an aromatic ring. The encapsulating resin composition according to any one of claims 1 to 3, wherein the non-polar polymer includes a styrene polymer. A support member,
An element arranged on the support member,
A cured product of the encapsulating resin composition according to any one of claims 1 to 4, which encapsulates the element,
Electronic component device. Placing the element on a support member,
A step of encapsulating the element with the encapsulating resin composition according to any one of claims 1 to 5,
And a method for manufacturing an electronic component device including.