KR20220025804A - Resin composition for sealing, electronic component device, and manufacturing method of electronic component device - Google Patents

Abstract

A resin composition for sealing, comprising an epoxy resin and a curing agent containing an active ester compound, wherein an equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) is 0.9 or less.

Description

Resin composition for sealing, 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 method for manufacturing an electronic component device.

The amount of transmission loss caused by thermal conversion of radio waves transmitted for communication in the dielectric is expressed as the product of the square root of the frequency and the relative permittivity and the dielectric loss tangent. That is, since the transmission signal is easily converted to heat in proportion to the frequency, the material of the communication member is required to have low dielectric properties as the frequency increases in order to suppress transmission loss.

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

Japanese Patent Laid-Open No. 2012-246367 Japanese Patent Laid-Open No. 2014-114352

In the field of information and communication, the frequency of radio waves is increasing with an increase in the number of channels and an increase in the amount of information to be transmitted. At present, examination of the 5th generation mobile communication system (5G) is progressing worldwide, and several of the range of about 30 GHz to 70 GHz are exemplified 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, the material used for manufacturing the communication member is required to have a further lower dielectric loss tangent.

In addition, these materials need to satisfy process applicability in the manufacturing process of the package. For example, a redistribution layer may be formed after sealing a board|substrate and a chip|tip with the resin composition for sealing at the time of semiconductor package manufacture, and alkaline solution is used in that case. However, the resin composition for sealing using an active ester compound as a hardening|curing agent has room for improvement in chemical-resistance with respect to an alkaline solution.

The present invention has been made in view of the above circumstances, and a resin composition for sealing from which a cured product having a low dielectric loss tangent and excellent chemical resistance is obtained, an electronic component device sealed using the same, and a method for manufacturing an electronic component device sealed using the same The task is to provide

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

<1> A resin composition for sealing, comprising an epoxy resin and a curing agent containing an active ester compound, wherein an equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) is 0.9 or less.

<2> The resin composition for sealing according to <1>, wherein an equivalent ratio (active ester compound/epoxy resin) of the active ester compound to the epoxy resin is 0.5 or more.

<3> The resin composition for sealing according to <1> or <2>, wherein an equivalent ratio of the entire curing agent to the epoxy resin (total curing agent/epoxy resin) is 0.5 to 1.2.

<4> Electronic component device provided with a support member, the element arrange|positioned on the said support member, and the hardened|cured material of the resin composition for sealing in any one of <1>-<3> which is sealing the said element. .

<5> A manufacturing method of an electronic component device including the process of arrange|positioning an element on a support member, and the process of sealing the said element with the resin composition for sealing in any one of <1>-<3>.

ADVANTAGE OF THE INVENTION According to this indication, the resin composition for sealing from which the hardened|cured material with a low dielectric loss tangent and excellent chemical resistance is obtained, the electronic component device sealed using this, and the manufacturing method of the electronic component device sealing using this are provided.

In the present disclosure, the word "process" includes, in addition to a process independent from other processes, if the objective of the process is achieved, even if it cannot be clearly distinguished from other processes, the said process is also included.

In the present disclosure, in the numerical range indicated using "to", the numerical values described before and after "to" are included as the minimum and maximum values, respectively.

In the numerical range described step by step in the present disclosure, the upper limit or lower limit described in one numerical range may be substituted with the upper limit or lower limit of the numerical range described in another step. In addition, in the numerical range described in this indication, you may substitute the upper limit or lower limit of the numerical range with the value shown in an Example.

In this indication, each component may contain the applicable substance multiple types. When a plurality of substances corresponding to each component exist in the composition, the content or content of each component means the total content or content of the plurality of substances present in the composition unless otherwise specified.

In this indication, the particle|grains corresponding to each component may contain multiple types. When a plurality of types of particles corresponding to each component exist in the composition, the particle diameter of each component means a value relating to a mixture of the plurality of types of particles present in the composition, unless otherwise specified.

In the present disclosure, the "active ester compound" refers to a compound having one or more ester groups (active ester groups) capable of reacting with an epoxy group in one molecule and having a curing action of an epoxy resin.

<Resin composition for sealing>

The resin composition for sealing of the present disclosure contains an epoxy resin and a curing agent including an active ester compound, and the equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) is 0.9 or less. It is a resin composition for sealing. .

As a result of examination of the present inventors, it turned out that the hardened|cured material obtained by hardening|curing the resin composition for sealing which has the said structure has a low dielectric loss tangent and is excellent in chemical-resistance. Although the reason is not necessarily clear, it thinks as follows.

First, the resin composition for sealing of the present disclosure contains an active ester compound as a curing agent. A phenol curing agent, an amine curing agent, and the like, which are generally used as curing agents for epoxy resins, generate secondary hydroxyl groups in reaction with the epoxy resin. In contrast, in the reaction between the epoxy resin and the active ester compound, an ester group having a lower polarity than that of a secondary hydroxyl group is generated. For this reason, the resin composition for sealing of this indication can suppress the dielectric loss tangent of hardened|cured material low compared with the resin composition for sealing containing only the hardening|curing agent which generate|occur|produces a secondary hydroxyl group.

Moreover, the resin composition for sealing of this indication is excellent in chemical-resistance compared with the resin composition for sealing whose equivalent ratio with respect to the epoxy resin of an active ester compound exceeds 0.9. Although the reason is not necessarily clear, it thinks as follows.

In the resin composition for sealing using the active ester compound as a hardening|curing agent of an epoxy resin, an ester group is produced|generated in hardened|cured material by reaction of an epoxy group and an active ester group. Since the ester group is hydrolyzed under alkaline conditions, it is thought that it becomes a cause of the fall of chemical-resistance property. In the resin composition for sealing of this indication, the number of active ester groups with respect to an epoxy group is suppressed to a certain level or less. For this reason, production|generation of the ester group by reaction of an epoxy group and an active ester group is suppressed, and it is thought that favorable chemical-resistance is maintained.

From the viewpoint of obtaining good chemical resistance, the equivalent ratio of the active ester compound to the epoxy resin in the sealing resin composition (active ester compound/epoxy resin) may be 0.8 or less, or 0.7 or less.

The lower limit in particular of the equivalent ratio (active ester compound/epoxy resin) of the active ester compound with respect to the epoxy resin in the resin composition for sealing is not restrict|limited. From a viewpoint of reducing the dielectric loss tangent of hardened|cured material, 0.5 or more may be sufficient and 0.6 or more may be sufficient.

The resin composition for sealing of this indication may contain only the active ester compound as a hardening|curing agent, and may further contain hardening agents (phenol hardening agent, an amine hardening agent, acid anhydride hardening|curing agent, etc.) other than an active ester compound. When the resin composition for sealing contains an active ester compound as a curing agent and a curing agent other than the active ester compound, the equivalent ratio of the entire curing agent to the epoxy resin (total curing agent/epoxy resin) is not particularly limited. For example, you may exist in the range of 0.5-1.2.

The resin composition for sealing of the present disclosure contains an epoxy group that does not react with the active ester group because the equivalent ratio of the active ester compound to the epoxy resin is 0.9 or less. The epoxy group which does not react with the active ester group may react with a functional group (hydroxyl group, etc.) of a hardening|curing agent other than an active ester compound, and may generate|occur|produce the self-polymerization reaction of an epoxy group. The self-polymerization reaction of the epoxy group proceeds prior to the reaction of the epoxy group and the active ester group to generate an ether bond. Since the ether bond is not hydrolyzed under alkaline conditions, good chemical resistance is maintained.

(epoxy resin)

The type of the epoxy resin contained in the resin composition for sealing of the present disclosure is not particularly limited.

Specific examples of the epoxy resin include phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. A novolak-type epoxy resin obtained by condensing or co-condensing at least one phenolic compound selected from phenol novolak-type epoxy resins, orthocresol novolac-type epoxy resins, etc.); a triphenylmethane-type epoxy resin obtained by epoxidizing a triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst; a copolymerization type epoxy resin obtained by epoxidizing a novolak resin obtained by cocondensing the phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; diphenylmethane type epoxy resins which are diglycidyl ethers, such as bisphenol A and bisphenol F; Biphenyl type epoxy resin which is diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a stilbene-type epoxy resin that is a diglycidyl ether of a stilbene-based phenol compound; sulfur atom-containing epoxy resins that are diglycidyl ethers such as bisphenol S; Epoxy resins which are glycidyl ethers of alcohols, such as butanediol, polyethyleneglycol, and polypropylene glycol; Glycidyl ester type epoxy resin which is glycidyl ester of polyhydric carboxylic acid compounds, such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins in which active hydrogen bonded to a nitrogen atom, such as aniline, diaminodiphenylmethane, or isocyanuric acid, is substituted with a glycidyl group; a dicyclopentadiene type epoxy resin obtained by epoxidizing a cocondensation resin of dicyclopentadiene and a phenol compound; Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5, which is an epoxidized olefin bond in the molecule alicyclic epoxy resins such as ,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; para-xylylene-modified epoxy resin which is a glycidyl ether of para-xylylene-modified phenol resin; a metaxylylene-modified epoxy resin that is a glycidyl ether of a metaxylylene-modified phenol resin; Terpene-modified epoxy resins which are glycidyl ethers of terpene-modified phenolic resins; dicyclopentadiene-modified epoxy resins which are glycidyl ethers of dicyclopentadiene-modified phenol resins; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers of polycyclic aromatic ring-modified phenol resins; Naphthalene-type epoxy resin which is glycidyl ether of a naphthalene ring containing phenol resin; Halogenated phenol novolak type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with peracids, such as peracetic acid; and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin. Furthermore, the epoxidized material of an acrylic resin, etc. are mentioned as an epoxy resin. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

The epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited. From a viewpoint of various characteristic balance, such as a moldability, reflow resistance, and electrical reliability, it is preferable that they are 100 g/eq - 1000 g/eq, and it is more preferable that they are 150 g/eq - 500 g/eq.

Let the epoxy equivalent of an epoxy resin be the value measured by the method according to JISK7236:2009.

The softening point or melting point of the epoxy resin is not particularly limited. From a viewpoint of moldability and reflow resistance, it is preferable that it is 40 degreeC - 180 degreeC, and it is more preferable that it is 50 degreeC - 130 degreeC from a viewpoint of the handleability at the time of preparation of the resin composition for sealing.

The melting point or softening point of the epoxy resin is a value measured by the single cylinder rotational viscometer method described in JIS K 7234:1986 and JIS K 7233:1986.

It is preferable that it is 0.5 mass % - 50 mass % from viewpoints, such as intensity|strength, fluidity|liquidity, heat resistance, moldability, and, as for the content rate of the epoxy resin in the resin composition for sealing, it is more preferable that they are 2 mass % - 30 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 this indication may contain hardening|curing agents other than an active ester compound.

As mentioned above, the resin composition for sealing of this indication can suppress the dielectric loss tangent of hardened|cured material low by using an active ester compound as a hardening|curing agent.

In addition, since the polar group in the cured product enhances the water absorbency 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. And by suppressing the water absorption of the hardened|cured material, and ultimately suppressing the content _of H2O which is a polar molecule, the dielectric loss tangent of hardened|cured material can be suppressed lower. 0% - 0.35 % are preferable, as for the water absorption of hardened|cured material, 0 % - 0.30 % are more preferable, 0 % - 0.25 % are still more preferable. Here, the water absorption rate of the cured product is the mass increase rate determined by the pressure cooker test (121°C, 2.1 atm, 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 reacting 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.

As an active ester compound, the ester compound obtained from at least 1 type of aliphatic carboxylic acid and aromatic carboxylic acid, and at least 1 type of an aliphatic hydroxy compound and an aromatic hydroxy compound is mentioned, for example. The ester compound which uses an aliphatic compound as a component of polycondensation tends to be excellent in compatibility with an epoxy resin by having an aliphatic chain. The ester compound which uses an aromatic compound as a component of polycondensation exists in the tendency 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 the phenolic hydroxyl group of an aromatic hydroxy compound is mentioned. 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 diphenylsulfonic acid, are substituted with carboxy groups; A mixture of a monohydric phenol in which one hydrogen atom of an aromatic ring is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 hydrogen atoms in the aromatic ring are substituted with a hydroxyl group as a raw material is used as a raw material, and an aromatic carboxylic acid and an aromatic hydroxy group An aromatic ester obtained by a condensation reaction of a phenolic hydroxyl group of a compound is preferable. That is, the aromatic ester which has the structural unit derived from the said aromatic carboxylic acid component, the structural unit derived from the said monohydric phenol, and the structural unit derived from the said 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 nodated through an aliphatic cyclic hydrocarbon group, an aromatic dicarboxylic acid or a halide thereof, and an aromatic mono, which are described in Japanese Patent Application Laid-Open No. 2012-246367. and active ester resins having a structure obtained by reacting a hydroxy compound. As the said active ester resin, the compound represented by the following structural formula (1) is preferable.

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, Y is a benzene ring, It is 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, n represents the average of the number of repetitions and is 0.25 to 1.5.

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

As another specific example of an active ester compound, the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) which are described in Unexamined-Japanese-Patent No. 2014-114352 are 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 C 1 to 4 carbon atom. an ester-forming structural moiety (z1) or a hydrogen atom (z2) selected from the group consisting of a benzoyl or naphthoyl group substituted with an alkyl group, and an acyl group having 2 to 6 carbon atoms, and at least one of Z is an ester-forming structural moiety (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 C 1 to 4 carbon atom. an ester-forming structural moiety (z1) or a hydrogen atom (z2) selected from the group consisting of a benzoyl or naphthoyl group substituted with an alkyl group, and an acyl group having 2 to 6 carbon atoms, and at least one of Z is an ester-forming structural moiety (z1).

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

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

You may use a commercial item as an active ester compound. Examples of commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; As an active ester compound containing an aromatic structure, "EXB9416-70BK", "EXB-8", "EXB-9425" (made by DIC Corporation); As an active ester compound containing the acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (made by Mitsubishi Chemical Corporation) etc. are mentioned as an active ester compound containing the benzoyl compound of phenol novolak.

An active ester compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The ester equivalent (molecular weight/number of active ester groups) of the active ester compound is not particularly limited. From the viewpoint of balance of various characteristics 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 is further desirable.

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

A hardening|curing agent may also contain other hardening|curing agents other than an active ester compound. In this case, the kind in particular of another hardening|curing agent is not restrict|limited, According to the desired characteristic etc. of the resin composition for sealing, it can select. Examples of the other curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent.

Specific examples of the phenol curing agent include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; From the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene a novolak-type phenolic resin obtained by condensing or co-condensing at least one selected phenolic compound with an aldehyde compound such as formaldehyde, acetaldehyde and propionaldehyde under an acidic catalyst; Aralkyl-type phenol resins, such as a phenol aralkyl resin synthesize|combined from the said phenolic compound, dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc., and a naphthol aralkyl resin; para-xylylene-modified phenol resin, meta-xylylene-modified phenol resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol resin synthesized by copolymerization from the phenolic compound and dicyclopentadiene; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl type phenol resin; a triphenylmethane type phenol resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst; The phenol resin obtained by copolymerizing these 2 or more types, etc. are mentioned. These phenol hardening|curing agents may be used individually by 1 type, and may be used in combination of 2 or more type.

The functional group equivalent of other curing agents (hydroxyl equivalent in the case of a phenol curing agent) is not particularly limited. From a viewpoint of various characteristic balance, such as a moldability, reflow resistance, electrical reliability, it is preferable that they are 70 g/eq - 1000 g/eq, and it is more preferable that they are 80 g/eq - 500 g/eq.

The functional group equivalent (in the case of a phenol curing agent, a hydroxyl group equivalent) of another hardening|curing agent shall be the value measured by the method according to JISK0070:1992.

The softening point or melting point of the curing agent is not particularly limited. From a viewpoint of moldability and reflow property, it is preferable that it is 40 degreeC - 180 degreeC, and it is more preferable that it is 50 degreeC - 160 degreeC from a viewpoint of the handleability at the time of manufacture of the resin composition for sealing.

The melting point or softening point of the curing agent is a value measured by the single cylinder rotational viscometer method described in JIS K 7234:1986 and JIS K 7233:1986.

The content of the active ester compound with respect to the total mass of the active ester compound and other curing agent is preferably 50 mass % or more, more preferably 60 mass % or more, and 70 mass % or more from the viewpoint of suppressing the dielectric loss tangent of the cured product low. more preferably.

The total content of the epoxy resin and the active ester compound with respect to the total mass of the epoxy resin, the active ester compound, and the other curing agent is preferably 70 mass % or more, and more preferably 75 mass % or more from the viewpoint of suppressing the dielectric loss tangent of the cured product low. It is preferable, and it is still more preferable that it is 80 mass % or more.

(curing accelerator)

The resin composition for sealing may contain a hardening accelerator. The type of the curing accelerator is not particularly limited, and may be selected according to the type of the epoxy resin or curing agent, desired characteristics of the resin composition for sealing, 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), 2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylhydroxyimidazole, 2-hepta Cyclic amidine compounds, such as decylimidazole; derivatives of the cyclic amidine compounds; a phenol novolac salt of the cyclic amidine compound or a derivative thereof; Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dime quinone compounds such as oxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone; and π bonds such as diazophenylmethane a compound having intramolecular polarization formed by adding a compound having; Cyclic amidinium compounds, such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide; Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, tertiary phosphines such as dialkylarylphosphine and alkyldiarylphosphine; a phosphine compound such as a complex of the tertiary phosphine and organic boron; The tertiary phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethyl Quinone compounds such as benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazo a compound having intramolecular polarization formed by adding a compound having a π bond, such as phenylmethane; 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-iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5- Dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo- a compound having intramolecular polarization obtained by reacting a halogenated phenol compound such as 4'-hydroxybiphenyl, followed by a process of dehydrohalogenation; tetra-substituted phosphonium, such as tetraphenylphosphonium; tetra-substituted phosphonium, and tetra-substituted borate, such as tetra-p-tolylborate; A salt of tetraphenylphosphonium and a phenol compound, etc. are mentioned.

When the resin composition for sealing contains a curing accelerator, the amount is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass, based on 100 parts by mass of the resin component (total amount of the epoxy resin and the curing agent). Do. 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, it tends to be satisfactorily cured in a short time. When 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 rate is not too fast and a good molded article tends to be obtained.

(Inorganic filling material)

The resin composition for sealing of this indication may contain an inorganic filler. The type of the inorganic filler is not particularly limited. Specific examples thereof include inorganic materials such as fused silica, crystalline silica, glass, alumina, aluminum nitride, boron nitride, talc, clay, and mica. You may use the inorganic filler which has a flame retardant effect. As an inorganic filler which has a flame retardant effect, composite metal hydroxides, such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate, etc. are mentioned.

Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. As a form of an inorganic filler, powder, the bead which made the powder spheroidized, fiber, etc. are mentioned.

When the inorganic filler is in the form of particles, the average particle diameter thereof is not particularly limited. For example, it is preferable that they are 0.2 micrometer - 100 micrometers of average particle diameter, and it is more preferable that they are 0.5 micrometer - 50 micrometers. It exists in the tendency for the viscosity raise of the resin composition for sealing to be suppressed more that an average particle diameter is 0.2 micrometer or more. When the average particle diameter is 100 µm or less, the filling properties tend to be more improved. The average particle diameter of an inorganic filler is calculated|required as a volume average particle diameter (D50) with a laser scattering diffraction method particle size distribution analyzer.

The content rate in particular of the inorganic filler contained in the resin composition for sealing is not restrict|limited. From a viewpoint of fluidity and strength, it is preferable that it is 30 volume% - 90 volume% of the whole resin composition for sealing, It is more preferable that it is 35 volume% - 85 volume%, It is more preferable that it is 40 volume% - 80 volume% . When the content rate of the inorganic filler is 30% by volume or more of the total resin composition for sealing, properties such as a coefficient of thermal expansion, thermal conductivity, and elastic modulus of the cured product tend to be improved more. When the content of the inorganic filler is 90% by volume or less of the total resin composition for sealing, the increase in the viscosity of the resin composition for sealing is suppressed, the fluidity is more improved, and the moldability tends to be more favorable.

[Various additives]

In addition to the components mentioned above, the resin composition for sealing may contain various additives, such as a coupling agent illustrated below, an ion exchanger, a mold release agent, a flame retardant, and a coloring agent. The resin composition for sealing may contain various additives well-known in the said technical field as needed other than the additive illustrated below.

(Coupling agent)

The resin composition for sealing may also contain a coupling agent. It is preferable that the resin composition for sealing contains a coupling agent from a viewpoint of improving the adhesiveness of a resin component and an inorganic filler. Examples of the coupling agent include silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidesilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate compounds, and known coupling agents such as aluminum/zirconium-based compounds. A ring agent is mentioned.

When the resin composition for sealing contains a coupling agent, it is preferable that they are 0.05 mass parts - 15 mass parts with respect to 100 mass parts of inorganic fillers, and, as for the quantity of a coupling agent, it is more preferable that they are 0.1 mass parts - 10 mass parts. When the quantity of a coupling agent is 0.05 mass parts or more with respect to 100 mass parts of inorganic fillers, there exists a tendency for adhesiveness with a flame|frame to improve more. There exists a tendency for the moldability of a package to improve that the quantity of a coupling agent is 15 mass parts or less with respect to 100 mass parts of inorganic fillers.

(ion exchanger)

The resin composition for sealing may also contain an ion exchanger. It is preferable that the resin composition for sealing contains an ion exchanger from a viewpoint of improving the moisture resistance of the electronic component device provided with the element to be sealed, and high temperature stand-by characteristic. The ion exchanger is not particularly limited, and a conventionally known one 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. An ion exchanger may be used individually by 1 type, and may be used in combination of 2 or more type. 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 resin composition for sealing contains an ion exchanger, the content will not be restrict|limited in particular, if it is an amount sufficient to capture|acquire ions, such as a halogen ion. For example, it is preferable that it is 0.1 mass part - 30 mass parts with respect to 100 mass parts (total amount of an epoxy resin and a hardening|curing agent) of a resin component, and it is more preferable that they are 1 mass part - 10 mass parts.

(Release agent)

The resin composition for sealing may contain a mold release agent from a viewpoint of obtaining favorable mold release property with the metal mold|die at the time of shaping|molding. The release agent is not particularly limited, and a conventionally known one may be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid, and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, and the like. A mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type.

When the resin composition for sealing contains a mold release agent, 0.01 mass part - 10 mass parts are preferable with respect to 100 mass parts of resin components (total amount of an epoxy resin and a hardening|curing agent), and, as for the amount, 0.1 mass part - 5 mass parts are more preferable. When the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. There exists a tendency for more favorable adhesiveness to be acquired as it is 10 mass parts or less.

(flame retardant)

The resin composition for sealing may contain a flame retardant. The flame retardant is not particularly limited, and a conventionally known flame retardant may be used. Specific examples thereof include organic or inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, and a metal hydroxide. A flame retardant may be used individually by 1 type, and may be used in combination of 2 or more type.

When the resin composition for sealing contains a flame retardant, the amount in particular is not restrict|limited as long as it is an amount sufficient to acquire a desired flame retardant effect. For example, it is preferable that it is 1 mass part - 30 mass parts with respect to 100 mass parts (total amount of an epoxy resin and a hardening|curing agent) of a resin component, and it is more preferable that they are 2 mass parts - 20 mass parts.

(coloring agent)

The resin composition for sealing may also contain a coloring agent. As a coloring agent, well-known coloring agents, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a rostrum, bengala, are mentioned. Content of a coloring agent can be suitably selected according to the objective etc. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.

(Method for preparing the resin composition for sealing)

The preparation method in particular of the resin composition for sealing is not restrict|limited. As a general method, after thoroughly mixing the components of a predetermined|prescribed compounding amount with a mixer etc., the method of melt-kneading with a mixing roll, an extruder, etc., cooling, and grinding|pulverization is mentioned. More specifically, for example, a method of uniformly stirring and mixing a predetermined amount of the above-described components, kneading with a kneader, roll, extruder, etc. previously heated to 70°C to 140°C, cooling, and pulverization can be heard

It is preferable that the resin composition for sealing is solid in normal temperature and under normal pressure (for example, 25 degreeC, under atmospheric pressure). The shape in particular when the resin composition for sealing is solid is not restrict|limited, A powder form, a granular form, tablet form, etc. are mentioned. It is preferable from the viewpoint of handleability that the size and mass in the case where the resin composition for sealing is in the form of a tablet has a size and mass that match the molding conditions of the package.

<Electronic component device>

The electronic component device which is one Embodiment of this indication is equipped with the hardened|cured material of the resin composition for sealing of this indication which is sealing the element and the said element.

As an electronic component device, an element (active element such as a semiconductor chip, a transistor, a diode, a thyristor, etc., a capacitor, a resistor, a coil, etc. What sealed the element part obtained by mounting a passive element etc. with the resin composition for sealing is mentioned.

More specifically, it has a structure in which the element is fixed on a lead frame, the terminal portion and the lead portion of the element such as a bonding pad are connected by wire bonding, bumps, etc., and then sealed by transfer molding or the like using a sealing resin composition. DIP(Dual Inline Package), PLCC(Plastic Leaded Chip Carrier), QFP(Quad Flat Package), SOP(Small Outline Package), SOJ(Small Outline J-lead package), TSOP(Thin Small Outline Package), TQFP(Thin general resin-sealed IC such as Quad Flat Package); TCP (Tape Carrier Package) which has the structure which sealed the element connected to the tape carrier by bump with the resin composition for sealing; COB (Chip On Board) module, hybrid IC, multi-chip module, etc. which have a structure in which the element connected to the wiring formed on the support member by wire bonding, flip-chip bonding, solder, etc. is sealed with the resin composition for sealing; Having a structure in which an element is mounted on the surface of a support member having a terminal for wiring board connection formed on the back side, and wiring formed on the element and the support member is connected by bump or wire bonding, and then the element is sealed with a sealing resin composition. BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc. are mentioned. Moreover, also in a printed wiring board, the resin composition for sealing can be used suitably.

<Manufacturing method of electronic component device>

The manufacturing method of the electronic component device of this indication includes the process of arrange|positioning an element on a support member, and the process of sealing the said element with the resin composition for sealing of this indication.

The method in particular of implementing each said process is not restrict|limited, It can carry out by a general method. In addition, the kind in particular of the support member and element used for manufacture of an electronic component device is not restrict|limited, The support member and element normally used for manufacture of an electronic component device can be used.

As a method of sealing an element using the resin composition for sealing of this indication, the low pressure transfer molding method, the injection molding method, the compression molding method, etc. are mentioned. Among these, the low-pressure transfer molding method is common.

Example

Hereinafter, although an Example demonstrates the said embodiment concretely, the scope of the said embodiment is not limited to these Examples.

<Preparation of the resin composition for sealing>

The components shown below were mixed at the compounding ratio (part by mass) shown in Table 1, and the resin composition for sealing of an Example and a comparative example was prepared.

・Epoxy resin 1: triphenylmethane type epoxy resin, epoxy equivalent 167 g/eq (Mitsubishi Chemical Co., Ltd., product name “1032H60”)

・Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 186 g/eq (Mitsubishi Chemical Co., Ltd., product name “YX-4000”)

Curing agent 1: Active ester compound manufactured by DIC Corporation

・Curing agent 2: Phenolic curing agent manufactured by Meiwa Chemicals Co., Ltd., product name “MEHC7851-SS”

Curing accelerator 1: 2-ethyl-4-methylimidazole (Shikoku Chemical Co., Ltd.)

Curing accelerator 2: triphenylphosphine/p-benzoquinone adduct

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

-Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")

・Releasing agent: montanic acid ester wax (Clariant Japan Co., Ltd., product name “HW-E”)

・Colorant: carbon black (Mitsubishi Chemical Co., Ltd., product name “MA600”)

· Filler 1: Fused silica (volume average particle size 6 μm)

-Filler 2: Fused silica (volume average particle diameter 0.6 µm)

-Filler 3: Fused silica (volume average particle diameter of 11.2 µm)

<Evaluation of the performance of the sealing resin composition>

(Measurement of dielectric constant and dielectric loss tangent)

The resin composition for sealing is put 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, post-curing is performed at 175° C. for 6 hours, and a plate-shaped cured product (length 12.5 mm, width 25 mm, thickness of about 0.2 mm) was obtained. Using a plate-shaped cured product as a test piece, the 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”).

(Spiral flow test)

Using a mold for spiral flow measurement conforming to 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 120 seconds to determine the flow distance (inch).

(Liquid resistance test)

The resin composition for sealing is put into a transfer molding machine, 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, post-curing is performed at 175 ° C. for 6 hours, and a rod-shaped cured product (5 mm × 5 mm × 20 mm) ) was obtained. The rod-shaped cured product was used as a test piece, and it was immersed in a mixed solution of DMSO (dimethyl sulfoxide)/TMAH (tetramethylammonium hydroxide, 25% AQ.) = 92/8 (mass ratio) under conditions of 80°C for 1 hour. On the basis of the mass before immersion, the residual ratio (mass %) was computed by the following formula from the mass of the test piece 1 hour after.

Residual ratio (mass %) = (mass after immersion (g)/mass before immersion (g)) x 100

As shown in Table 1, the resin composition for sealing containing an active ester compound as a curing agent had a lower dielectric loss tangent value of the cured product than the resin composition for sealing of Comparative Example 1 which did not contain an active ester compound as a curing agent.

The resin composition for sealing of Examples containing an active ester compound as a curing agent and having an equivalent ratio of the active ester compound to the epoxy resin of 0.9 or less, the resin composition for sealing of Comparative Example 2 in which the equivalent ratio of the active ester compound to the epoxy resin is 1.0 Compared to that, the chemical resistance of the cured product was excellent.

As for the indication of Japanese Patent Application No. 2019-118699, the whole is taken in into this specification by reference.

All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference.

Claims (5)

A resin composition for sealing, comprising an epoxy resin and a curing agent containing an active ester compound, wherein an equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) is 0.9 or less. The resin composition for sealing according to claim 1, wherein the equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) is 0.5 or more. The resin composition for sealing according to claim 1 or 2, wherein an equivalent ratio of the entire curing agent to the epoxy resin (total curing agent/epoxy resin) is 0.5 to 1.2. An electronic component device comprising a support member, an element disposed on the support member, and a cured product of the resin composition for sealing according to any one of claims 1 to 3 sealing the element. The manufacturing method of an electronic component device including the process of arrange|positioning an element on a support member, and the process of sealing the said element with the resin composition for sealing in any one of Claims 1-3.