WO2020262654A1

WO2020262654A1 - Sealing resin composition, electronic component device, and method for manufacturing electronic component device

Info

Publication number: WO2020262654A1
Application number: PCT/JP2020/025356
Authority: WO
Inventors: 貴大齋藤; 格山浦; 圭一春日
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2019-06-26
Filing date: 2020-06-26
Publication date: 2020-12-30
Also published as: KR20220025804A; TW202108655A; CN114008105A; JPWO2020262654A1

Abstract

A sealing resin composition according to the present invention contains an epoxy resin and a curing agent including an active ester compound, the equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) being 0.9 or less.

Description

Manufacturing method of sealing resin composition, electronic component device and electronic component device

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

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

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

Japanese Unexamined Patent Publication No. 2012-246367 Japanese Unexamined Patent Publication No. 2014-114352

In the information and communication field, radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases. Currently, the 5th generation mobile communication system (5G) is being studied worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material used for manufacturing communication members is required to have a lower dielectric loss tangent.
In addition, these materials must meet process applicability in the packaging process. For example, when manufacturing a semiconductor package, a substrate and a chip may be sealed with a sealing resin composition and then a rewiring layer may be formed, and an alkaline solution is used at that time. However, there is room for improvement in the chemical resistance of the sealing resin composition using the active ester compound as a curing agent to an alkaline solution.

The present invention has been made in view of the above circumstances, a sealing resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent chemical resistance, an electronic component device sealed using the same, and the like. It is an object of the present invention to provide a method for manufacturing an electronic component device to be sealed by using.

Specific means for solving the above problems include the following aspects.
<1> A sealing resin containing an epoxy resin and a curing agent containing an active ester compound, wherein the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin is 0.9 or less. Composition.
<2> The sealing resin composition according to <1>, wherein the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin is 0.5 or more.
<3> The sealing resin composition according to <1> or <2>, wherein the equivalent ratio of the entire curing agent to the epoxy resin (total curing agent / epoxy resin) is 0.5 to 1.2.
<4> The cured product of the sealing resin composition according to any one of <1> to <3>, which seals the support member, the element arranged on the support member, and the element. And electronic component equipment.
<5> An electronic component device including a step of arranging the element on a support member and a step of sealing the element with the sealing resin composition according to any one of <1> to <3>. Manufacturing method.

According to the present disclosure, a sealing resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent chemical resistance, an electronic component device sealed using the resin composition, and an electronic component sealed using the same. A method of manufacturing the device is provided.

In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
In the present disclosure, the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. 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 contain a plurality of applicable substances. When a plurality 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 plurality 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 contained. When a plurality 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 particles present in the composition unless otherwise specified.

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

<Resin composition for sealing>
The sealing resin composition of the present disclosure contains an epoxy resin and a curing agent containing 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. The following is a sealing resin composition.

As a result of the studies by the present inventors, it was found that the cured product obtained by curing the sealing resin composition having the above structure has a low dielectric loss tangent and excellent chemical resistance. The reason is not always clear, but it can be 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, etc., 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 having a polarity lower than that of the secondary hydroxyl group is generated. Therefore, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to be lower than that of the sealing resin composition containing only a curing agent that generates a secondary hydroxyl group.

Further, the sealing resin composition of the present disclosure is superior in chemical resistance to the sealing resin composition in which the equivalent ratio of the active ester compound to the epoxy resin exceeds 0.9. The reason is not always clear, but it can be considered as follows.

In a sealing resin composition using an active ester compound as a curing agent for an epoxy resin, an ester group is generated in the cured product by the reaction between the epoxy group and the active ester group. Since the ester group is hydrolyzed under alkaline conditions, it is considered to cause a decrease in chemical resistance. In the sealing resin composition of the present disclosure, the number of active ester groups relative to epoxy groups is suppressed to a certain level or less. Therefore, it is considered that the formation of ester groups due to the reaction between the epoxy group and the active ester group is suppressed, and good chemical resistance is maintained.

From the viewpoint of obtaining good chemical resistance, the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin in the sealing resin composition may be 0.8 or less, 0.7. It may be as follows.
The lower limit of the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin in the sealing resin composition is not particularly limited. From the viewpoint of reducing the dielectric loss tangent of the cured product, it may be 0.5 or more, or 0.6 or more.

The sealing resin composition of the present disclosure further contains a curing agent other than the active ester compound (phenol curing agent, amine curing agent, acid anhydride curing agent, etc.) even if it contains only an active ester compound as a curing agent. You may be. When the sealing resin composition 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, it may be in the range of 0.5 to 1.2.

The sealing resin composition 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 that does not react with the active ester group may react with a functional group (hydroxyl group or the like) of a curing agent other than the active ester compound, or may cause a self-polymerization reaction of the 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 form an ether bond. Since the ether bond does not hydrolyze under alkaline conditions, good chemical resistance is maintained.

(Epoxy resin)
The type of epoxy resin contained in the sealing resin composition of the present disclosure is not particularly limited.
Specifically, the epoxy resin is 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. A novolak type epoxy resin (phenol novolak type) which is an epoxy obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Epoxy resin, orthocresol novolac type epoxy resin, etc.); A triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxy resin; a copolymerized epoxy resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben-type epoxy resin which is a diglycidyl ether of a stillben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin such as diglycidyl ether such as S; epoxy resin which is glycidyl ether of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester type epoxy resin, which is a glycidyl ester of glycidyl ester; glycidylamine type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid is replaced with a glycidyl group; co-dicyclopentadiene and phenol compound Dicyclopentadiene type epoxy resin which is an epoxy of a condensed resin; vinylcyclohexene diepoxide which is an epoxy of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5 Alicyclic epoxy resin such as 5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene-modified epoxy resin which is glycidyl ether of paraxylylene-modified phenol resin; metaxylylene-modified epoxy resin which is glycidyl ether of metaxylylene-modified phenol resin Terpen-modified epoxy resin, which is a glycidyl ether of terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin, which is a glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of a ring-aromatic ring-modified phenol resin; naphthalene-type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; halogenated phenol novolac-type epoxy resin; hydroquinone-type epoxy resin; trimethylol propane Type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl type epoxy resin obtained by epoxyizing an aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. ; And so on. Further, an epoxy resin such as an acrylic resin can be mentioned as an epoxy resin. These epoxy resins may be used individually by 1 type or 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 the viewpoint of balance of various properties such as moldability, reflow resistance and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

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

The softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C.

The melting point or softening point of the epoxy resin shall be 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 epoxy resin in the sealing resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. More preferably.

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

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

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

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

Examples of the active ester compound include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds containing an aliphatic compound as a component of polycondensation tend to have excellent compatibility with an epoxy resin because they have an aliphatic chain. Ester compounds containing an aromatic compound as a component of polycondensation tend to have excellent heat resistance due to having an aromatic ring.

Specific examples of the active ester compound include an aromatic ester obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group of an aromatic hydroxy compound. 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 a carboxy group, and the hydrogen atom of the aromatic ring described above. A mixture of a monovalent phenol in which one of the above is substituted with a hydroxyl group and a polyvalent phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group as a raw material, and an aromatic carboxylic acid and an aromatic hydroxy compound An aromatic ester obtained by a condensation reaction with a phenolic hydroxyl group is preferable. 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 described in JP2012-246367, and an aromatic dicarboxylic acid or Examples thereof include an active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound. As the active ester resin, a compound represented by the following structural formula (1) is preferable.

In the structural formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms, and 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, 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 number of repetitions. It is 25 to 1.5.

Specific examples of the compound represented by the 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, the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) described in JP-A-2014-114352 can be used. Can be mentioned.

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

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

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

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

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

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

The ester equivalent (molecular weight / number of active ester groups) of the active ester compound is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferable, 170 g / eq to 300 g / eq is more preferable, and 200 g / eq to 250 g / eq is preferable. More preferred.

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

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

Specific examples of the phenol curing agent include polyvalent phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol. , Aminophenol and other phenolic compounds and at least one phenolic compound selected from the group consisting of α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde as acidic catalysts. Novolac-type phenolic resin obtained by condensing or co-condensing underneath; phenol-aralkyl resin synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc., naphthol-aralkyl resin, etc. Paraxylylene-modified phenolic resin, metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpen-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol synthesized by copolymerization of the above phenolic compound and dicyclopentadiene. Resin; Cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type phenolic resin to be used; phenolic resin obtained by copolymerizing two or more of these types can be mentioned. These phenol curing agents may be used alone or in combination of two or more.

The functional group equivalents of other curing agents (hydroxyl equivalents in the case of phenol curing agents) are not particularly limited. From the viewpoint of balance of various characteristics 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.

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

The softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 160 ° C. ..

The melting point or softening point of the curing agent shall be 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 agents is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of suppressing the dielectric adjacency of the cured product to be low. It is preferably 70% by mass or more, and more preferably 70% by mass or more.

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 other curing agents is preferably 70% by mass or more, preferably 75% by mass, from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably% or more, and even more preferably 80% by mass or more.

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

Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonen-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, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylhydroxyimidazole, 2-heptadecylimidazole; Derivatives of cyclic amidin compounds; phenol novolac salts of the cyclic amidin compounds or derivatives thereof; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone. , 2,6-Didimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, diazophenyl Compounds with intramolecular polarization formed by adding a compound having a π bond, such as methane; DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N -Cyclic amidinium compounds such as tetraphenylborate salt of methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; Derivatives of amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; triphenylphosphine, Diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkyl Phenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, archi Tertiary phosphine such as rudiarylphosphine; phosphine compound such as a complex of the tertiary phosphine and organic borons; the tertiary phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl- A quinone compound such as 1,4-benzoquinone, a compound having an intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromo Phenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodide phenol, 3-iodide phenol, 2-iodide 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- It is obtained by reacting a halogenated phenol compound such as naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and then through a step of dehalogenating hydrogen. Compounds with intramolecular polarization; tetra-substituted phosphoniums such as tetraphenylphosphonium, tetra-substituted phosphoniums and tetra-substituted borates having no phenyl group bonded to boron atoms such as tetra-p-tolylbolate; salts of tetraphenylphosphonium and phenol compounds And so on.

When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and 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 part by mass or more with respect to 100 parts by mass of the resin component, it tends to cure well 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 product tends to be obtained.

(Inorganic filler)
The sealing resin composition of the present disclosure may contain an inorganic filler. The type of 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. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.

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. As the inorganic filler, one type may be used alone or two or more types may be used in combination. Examples of the form of the inorganic filler include unpowdered beads, spherical beads of powder, fibers, and the like.

When the inorganic filler is in the form of particles, its 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, the increase in viscosity of the sealing 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 size of the inorganic filler is determined as the volume average particle size (D50) by a laser scattering diffraction method particle size distribution measuring device.

The content of the inorganic filler contained in the sealing resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 85% by volume, and 40% to 80% by volume of the entire sealing resin composition. It is more preferably%. When the content of the inorganic filler is 30% by volume or more of the entire sealing resin composition, the properties such as the coefficient of thermal expansion, 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 sealing resin composition, an increase in the viscosity of the sealing resin composition is suppressed, the fluidity is further improved, and the moldability is improved. It tends to be.

[Various additives]
In addition to the above-mentioned components, the sealing resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, and a colorant exemplified below. The sealing 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 contain 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 silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 15 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably to 10 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 15 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 contain an ion exchanger. The sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, 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 sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part 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 (total amount of epoxy resin and curing agent).

(Release agent)
The sealing resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. As the release agent, one type may be used alone or two or more types may be used in combination.

When the sealing resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent), 0.1. More preferably, it is by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 part by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.

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

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

(Colorant)
The sealing resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose and the like. As the colorant, one type may be used alone or two or more types may be used in combination.

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

The sealing resin composition is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). When the sealing resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the sealing resin composition is in the form of a tablet, it is preferable that the size and mass match the molding conditions of the package from the viewpoint of handleability.

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

Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, and resistors. , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a sealing resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack), SOJ (SmallOdline) General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition. A COB (Chip On Board) module, hybrid IC, or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a sealing resin composition. Chip module, etc .; An element is mounted on the front surface of a support member having terminals for connecting a wiring plate on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, the sealing resin composition Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the sealing resin composition can also be preferably used in the printed wiring board.

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

The method of carrying out each of the above steps is not particularly limited, and can be carried out by a general method. Further, the types of support members and elements used in the manufacture of electronic component devices are not particularly limited, and support members and elements generally used in the manufacture of electronic component devices can be used.

Examples of the method for sealing the element using the sealing resin composition of the present disclosure include a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like. Of these, the low-pressure transfer molding method is common.

Hereinafter, the above-described embodiment will be specifically described with reference to Examples, but the scope of the above-mentioned Embodiment is not limited to these Examples.

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

-Epoxy resin 1: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
-Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 186 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

-Curing agent 1: Active ester compound manufactured by DIC Corporation-Curing agent 2: Phenol curing agent manufactured by Meiwa Kasei Co., Ltd., product name "MEHC7851-SS"
・ Curing accelerator 1: 2-ethyl-4-methylimidazole (Shikoku Kasei 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")
-Release agent: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")
-Filler 1: Fused silica (volume average particle size 6 μm)
-Paper 2: Fused silica (volume average particle size 0.6 μm)
Filler 3: Fused silica (volume average particle size 11.2 μm)

<Performance evaluation of sealing resin composition>
(Measurement of relative permittivity and dielectric loss tangent)
The sealing 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. (12.5 mm in length, 25 mm in width, and about 0.2 mm in thickness) were obtained. Using a plate-shaped cured product as a test piece, the relative permittivity and dielectric loss tangent at 60 GHz were measured at a temperature of 25 ± 3 ° C. using a permittivity measuring device (Agilent, product name “Network Analyzer N5227A”).

(Spiral flow test)
Using a spiral flow measuring mold according 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, and the flow distance ( inch) was sought.

(Chemical resistance test)
The resin composition for sealing was charged 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, and post-cured at 175 ° C. for 6 hours to obtain a rod-shaped cured product ( 5 mm × 5 mm × 20 mm) was obtained. Using the rod-shaped cured product as a test piece, it was immersed in a mixed solution of DMSO (dimethyl sulfoxide) / TMAH (tetramethylammonium hydroxide, 25% AQ.) = 92/8 (mass ratio) at 80 ° C. for 1 hour. It was. The residual ratio (mass%) was calculated from the mass of the test piece after 1 hour based on the mass before immersion by the following formula.

Residual rate (mass%) = (mass after immersion (g) / mass before immersion (g)) × 100

As shown in Table 1, the sealing resin composition containing the active ester compound as the curing agent has a dielectric loss tangent of the cured product as compared with the sealing resin composition of Comparative Example 1 containing no active ester compound as the curing agent. The value of was low.
The sealing resin composition of the example, which contains an active ester compound as a curing agent and has an equivalent ratio of the active ester compound to the epoxy resin of 0.9 or less, has an equivalent ratio of the active ester compound to the epoxy resin of 1.0. Compared with the sealing resin composition of Comparative Example 2, the cured product was excellent in chemical resistance.

The entire disclosure of Japanese Patent Application No. 2019-18699 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated and incorporated herein.

Claims

A sealing resin composition containing an epoxy resin and a curing agent containing an active ester compound, wherein the equivalent ratio of the active ester compound to the epoxy resin (active ester compound / epoxy resin) is 0.9 or less.
The sealing resin composition according to claim 1, wherein the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin is 0.5 or more.
The sealing resin composition according to claim 1 or 2, wherein the equivalent ratio of the entire curing agent to the epoxy resin (total curing agent / epoxy resin) is 0.5 to 1.2.
A support member, an element arranged on the support member, and a cured product of the sealing resin composition according to any one of claims 1 to 3, which seals the element. Electronic component equipment to be equipped.
A method for manufacturing an electronic component device, comprising a step of arranging the element on a support member and a step of sealing the element with the sealing resin composition according to any one of claims 1 to 3. ..