TWI801371B - Epoxy resin composition and electronic component device - Google Patents

Abstract

An epoxy resin composition includes a monofunctional epoxy compound having one epoxy group in a molecule, a multifunctional epoxy compound having two or more epoxy groups in a molecule, and a curing agent. A curable resin composition includes a curable resin, a curing agent, and a compound having a (meth)acryloyl group. An electronic component device includes an element sealed by the epoxy resin composition or the curable resin composition.

Description

Epoxy resin composition and electronic component device

The present invention relates to an epoxy resin composition, a curable resin composition and an electronic component device.

Along with recent miniaturization, weight reduction, performance enhancement, etc. of electronic equipment, the increase in mounting density has been promoted. As a result, the mainstream of electronic component devices is changing from conventional pin-insertion packages to surface-mount packages such as integrated circuits (Integrated Circuit, IC) and large scale integrated circuits (Large Scale Integration, LSI).

The mounting method of the surface mount type package is different from the existing pin insertion type package. That is, when mounting pins on a wiring board, conventional pin-insertion-type packages insert pins into the wiring board and solder from the back of the wiring board, so the package is not directly exposed to high temperatures. However, in the surface mount type package, the entire electronic component device is processed with a solder bath, a reflow apparatus, etc., and therefore the package is directly exposed to soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture will rapidly expand due to moisture absorption during soldering, and the generated vapor pressure will act as peeling stress, causing peeling between the interposer such as components and lead frames and the sealing material. This may cause package cracks, poor electrical characteristics, and the like. Therefore, development of a sealing material excellent in adhesiveness to an interposer and also excellent in solder heat resistance (reflow resistance) has been desired.

In order to meet these demands, from the viewpoint of reducing moisture absorption, various studies have been conducted on epoxy resins as main materials. In addition, from the viewpoint of improving the adhesion to interposers such as devices and lead frames, the use of silane coupling agents has been studied as a modifier of inorganic fillers contained in sealing materials. Specifically, the use of epoxy group-containing silane coupling agents or amino group-containing silane coupling agents (for example, refer to Patent Document 1), the use of sulfur atom-containing silane coupling agents (for example, refer to Patent Document 2), etc. .

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 11-147939

[Patent Document 2] Japanese Patent Laid-Open No. 2000-103940

However, currently, it is impossible to obtain a curable resin composition that sufficiently satisfies the reflow resistance for practical use.

The object of the first embodiment of the present disclosure is to provide an epoxy resin composition excellent in reflow resistance, and an electronic component device including an element sealed with the epoxy resin composition.

The object of the second embodiment of the present disclosure is to provide a curable resin composition excellent in reflow resistance, and an electronic component device including an element sealed with the curable resin composition.

Means for solving the above-mentioned problems include the following first embodiment.

<1> An epoxy resin composition comprising: a monofunctional epoxy compound having one epoxy group in one molecule; a multifunctional epoxy compound having two or more epoxy groups in one molecule; and hardener.

<2> The epoxy resin composition according to <1>, wherein the monofunctional epoxy compound includes a monofunctional epoxy compound having one alicyclic epoxy group in one molecule.

<3> The epoxy resin composition according to <1>, wherein the monofunctional epoxy compound includes a monofunctional epoxy compound having one acyclic epoxy group and one phenyl group in one molecule.

<4> The epoxy resin composition according to any one of <1> to <3>, wherein the content of the monofunctional epoxy compound is 1 mass part with respect to 100 parts by mass of the polyfunctional epoxy compound Parts ~ 30 parts by mass.

<5> The epoxy resin composition according to any one of <1> to <4>, which further contains a curing accelerator.

<6> The epoxy resin composition according to any one of <1> to <5>, which further contains an inorganic filler, and the content of the inorganic filler is relative to the total amount of the epoxy resin composition. The volume is 70% to 95% by volume.

<7> The epoxy resin composition according to any one of <1> to <6>, which further contains a silane coupling agent.

<8> An electronic component device including an element sealed with the epoxy resin composition according to any one of <1> to <7>.

Furthermore, means for solving the above-mentioned problems include the following second embodiment form.

<9> A curable resin composition containing a curable resin, a curing agent, and a compound having a (meth)acryl group.

<10> The curable resin composition according to <9>, wherein the molecular weight of the compound having a (meth)acryl group is 180-320.

<11> The curable resin composition according to <9> or <10>, wherein the compound having a (meth)acryl group includes a (meth)acrylate compound.

<12> The curable resin composition according to any one of <9> to <11>, wherein the compound having a (meth)acryl group has an alicyclic structure.

<13> The curable resin composition according to any one of <9> to <12>, wherein the compound having a (meth)acryl group has an epoxy group.

<14> The curable resin composition according to any one of <9> to <13>, wherein the compound having a (meth)acryl group has an alicyclic epoxy group.

<15> The curable resin composition according to any one of <9> to <14>, which further contains a curing accelerator.

<16> The curable resin composition according to any one of <9> to <15>, which further contains an inorganic filler, and the content of the inorganic filler is relative to the total amount of the curable resin composition. The volume is 70% to 95% by volume.

<17> The curable resin composition according to any one of <9> to <16>, which further contains a coupling agent.

<18> An electronic component device including an element sealed with the curable resin composition according to any one of <9> to <17>.

According to the first embodiment of the present disclosure, an epoxy resin composition excellent in reflow resistance, and an electronic component device including elements sealed with the epoxy resin composition can be provided.

According to the second embodiment of the present disclosure, a curable resin composition excellent in reflow resistance, and an electronic component device including elements sealed with the curable resin composition can be provided.

Hereinafter, the form for carrying out this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and do not limit the present invention.

In the present disclosure, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced by the upper limit or lower limit of the numerical range described in other stages. In addition, in the numerical range described in this indication, the upper limit or the lower limit of the numerical range may be replaced with the value shown in an Example.

In the present disclosure, each component may contain a plurality of equivalent substances. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the plurality of substances present in the composition.

In this disclosure, a plurality of particles corresponding to each component may be contained. When there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle size of each component refers to a value for a mixture of the plurality of types of particles present in the composition.

In this disclosure, "(meth)acryl" refers to at least one of acryl and methacryl, and "(meth)acryloxy" refers to acryloxy and methacryl. At least one of acryloxy groups, "(meth)acrylate" refers to at least one of acrylate and methacrylate, "(meth)acrylate" refers to acrylate and methacrylate at least one.

<Epoxy resin composition of the first embodiment>

The epoxy resin composition of the first embodiment contains (A) a monofunctional epoxy compound having one epoxy group in one molecule, (B) a polyfunctional epoxy compound having two or more epoxy groups in one molecule Oxygen compound, and (C) Hardener. The epoxy resin composition may further contain other components as necessary. Hereinafter, (A) the monofunctional epoxy compound which has one epoxy group in 1 molecule is also abbreviated as "monofunctional epoxy compound". In addition, (B) the polyfunctional epoxy compound which has two or more epoxy groups in 1 molecule is also abbreviated as "polyfunctional epoxy compound".

When the epoxy resin composition contains a monofunctional epoxy compound, an epoxy resin composition excellent in reflow resistance can be obtained. The detailed reason why an epoxy resin composition excellent in reflow resistance can be obtained by containing a monofunctional epoxy compound is not necessarily clear, but it is speculated that the reason is that epoxy resins that contain less monofunctional epoxy compounds as epoxy resins In terms of composition, the hardness of epoxy resin composition containing monofunctional epoxy compound The crosslink density in the compound decreases, and the high temperature elastic coefficient decreases. In general, from the viewpoint of peeling stress at the time of reflow, the lower the high-temperature modulus of elasticity, the more difficult it is for peeling to occur between the interposer and the sealing material, so it is considered that the reflow resistance is excellent. In addition, since the monofunctional epoxy compound has an epoxy group, it is considered that the reactivity is excellent, and the crosslinking density is lowered as described above to lower the modulus of elasticity, and on the other hand, the curability can be sufficiently maintained.

(A) Monofunctional epoxy compound

The epoxy resin composition contains a monofunctional epoxy compound. The monofunctional epoxy compound contained in an epoxy resin composition may be used individually by 1 type, and may use it in combination of 2 or more types.

The monofunctional epoxy compound is not particularly limited as long as it has one epoxy group in one molecule. The epoxy group contained in the monofunctional epoxy compound may be an alicyclic epoxy group such as an epoxy cyclohexyl group, or may be an acyclic epoxy group such as a glycidyl group. It is also possible to combine a monofunctional epoxy compound having one alicyclic epoxy group in one molecule (hereinafter, also referred to as a "monofunctional alicyclic epoxy compound"), and a monofunctional epoxy compound having one acyclic epoxy group in one molecule. A monofunctional epoxy compound (hereinafter, also referred to as a "monofunctional acyclic epoxy compound") of the epoxy group is used in combination. Hereinafter, (A1) monofunctional alicyclic epoxy compound and (A2) monofunctional acyclic epoxy compound are demonstrated respectively.

(A1) Monofunctional alicyclic epoxy compound

The monofunctional alicyclic epoxy compound will not be specifically limited if it is a monofunctional epoxy compound which has one alicyclic epoxy group in 1 molecule. The alicyclic epoxy group has an oxygen atom bonded to two adjacent carbon atoms constituting the cycloaliphatic skeleton.

The carbon number of the cycloaliphatic skeleton is not particularly limited. The cyclic aliphatic skeleton is, for example, preferably a 5-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and still more preferably a 6-membered ring.

The alicyclic structure may or may not contain an unsaturated bond, and may or may not have a substituent.

The monofunctional alicyclic epoxy compound is preferably a compound having an alicyclic epoxy group represented by the following general formula (a).

In the general formula (a), R represents a monovalent substituent not including an epoxy group, and n represents an integer of 0-10.

The monovalent substituent which does not contain an epoxy group represented by R is not specifically limited, A hydrocarbon group etc. are mentioned. As a hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group etc. are mentioned, These may have a substituent or may not have a substituent. Among these, an alkyl group is preferable, and a substituted alkyl group is more preferable. When there are plural Rs, the plural Rs may be the same or different.

n is preferably 1-4, more preferably 1.

When R is a substituted alkyl group, the substituent of the alkyl group is preferably a group having an ethylenically unsaturated double bond, more preferably a group having a (meth)acryloyl group, and further preferably a group having a (meth)acryl group. base) acryloyloxy group. In the case where the monofunctional alicyclic epoxy compound contains a group having an ethylenically unsaturated double bond as an alkyl substituent, the number of ethylenically unsaturated double bonds in the molecule of the monofunctional alicyclic epoxy compound It may be 1, or 2 or more.

As an example of a monofunctional alicyclic epoxy compound, the compound represented by following general formula (b) is mentioned.

In the general formula (b), R ¹ represents a hydrogen atom or a methyl group. R ² represents a monovalent substituent not containing an epoxy group. X represents a single bond or a divalent linking group. n represents an integer from 0 to 9.

R ¹ is preferably methyl.

The definition and preferred embodiment of R ² are the same as the definition and preferred embodiment of R in formula (a).

n is preferably 0-3, more preferably 0.

The divalent linking group in X is not particularly limited, and examples thereof include aliphatic hydrocarbon groups and the like. Examples of the aliphatic hydrocarbon group include linear or branched alkylene groups and the like. When X is an alkylene group, the number of carbons contained in the alkylene group is not particularly limited, but is preferably 1-10, more preferably 1-3, and still more preferably 1. The alkylene group may also have a substituent. In addition, the carbon number contained in the said alkylene group is set not including the carbon number contained in a branch or a substituent.

As an example of the monofunctional alicyclic epoxy compound represented by General formula (b), the compound represented by following formula (c) is mentioned.

[Chem 3]

As another example of the monofunctional alicyclic epoxy compound, the compound represented by following general formula (d) is mentioned.

In general formula (d), X represents a single bond or a divalent linking group. The divalent linking group in X is not particularly limited, and examples thereof include aliphatic hydrocarbon groups and the like. Examples of the aliphatic hydrocarbon group include linear or branched alkylene groups and the like. When X is an alkylene group, the number of carbons contained in the alkylene group is not particularly limited, and may be 1-10. The alkylene group may also have a substituent. In addition, the carbon number contained in the said alkylene group is set not including the carbon number contained in a branch or a substituent.

As an example of the monofunctional alicyclic epoxy compound represented by General formula (d), the compound represented by following formula (e) is mentioned.

(A2) Monofunctional acyclic epoxy compound

The monofunctional acyclic epoxy compound will not be specifically limited if it is a monofunctional epoxy compound which has one acyclic epoxy group in 1 molecule. A glycidyl group, a glycidyloxy group, etc. are mentioned as an acyclic epoxy group.

The monofunctional acyclic epoxy compound is preferably a monofunctional epoxy compound having one acyclic epoxy group and a phenyl group in one molecule. Examples of compounds having one acyclic epoxy group and phenyl group in one molecule include compounds having one glycidyl group and phenyl group in one molecule, compounds having one glycidyloxy group in one molecule Compounds with phenyl, etc. Among them, the monofunctional acyclic epoxy compound is preferably a compound represented by the following general formula (f).

In formula (f), R represents a monovalent substituent not including an epoxy group, and n represents an integer of 0-5.

The monovalent substituent not containing an epoxy group represented by R is not particularly limited, and examples thereof include hydrocarbon groups and the like. As a hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group etc. are mentioned. When R represents an alkyl group, the alkyl group may be linear or branched, may have a cyclic structure, and is preferably branched. When R represents an aryl group, the aryl group may have a substituent or may not have a substituent. When there are plural Rs, the plural Rs may be the same or different. The substitution position of R is not particularly limited, but is preferably an ortho position or a para position.

n is preferably 0-3, more preferably 0.

Examples of the compound represented by the general formula (f) include compounds represented by the following general formula (g) and general formula (h).

In formula (g), R represents a monovalent substituent not including an epoxy group, and n represents an integer of 0-4.

The definition and preferred embodiment of R in the compound represented by formula (g) are the same as the definition and preferred embodiment of R in the compound represented by formula (f).

n is preferably 0-2, more preferably 0.

In formula (h), R ¹ and R ² each independently represent a monovalent substituent not containing an epoxy group, p represents an integer of 0-4, and q represents an integer of 0-5.

The definition and preferred embodiment of the monovalent substituent not containing epoxy group represented by R ¹ and R ² are the same as the definition and preferred embodiment of R in formula (f).

p is preferably 0-2, more preferably 0. q is preferably 0-3, more preferably 0.

As a monofunctional epoxy compound, a synthesizer may be used, and a commercial item may be used. As a monofunctional epoxy compound, for example, 3,4-epoxycyclohexylmethyl methacrylate (for example, trade name: Cyclomer (CYCLOMER) M100, manufactured by Daicel Co., Ltd.), 4-third Butylphenyl glycidyl ether (e.g., trade name: ED-509S, manufactured by ADEKA), 2-biphenyl glycidyl ether (e.g., trade name: EX-142, manufactured by Nagase ChemteX ) Co., Ltd.), etc.

The monofunctional epoxy compound can be solid or liquid at normal temperature (25° C.), preferably liquid.

The epoxy equivalent of the monofunctional epoxy compound is not particularly limited. From the viewpoint of fluidity and reflow resistance, it is preferably at most 500 g/eq, more preferably at most 300 g/eq.

With respect to 100 parts by mass of the polyfunctional epoxy compound described later, the content of the monofunctional epoxy compound is preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, and further preferably 5 to 25 parts by mass. parts by mass, preferably 10 to 20 parts by mass. When content of a monofunctional epoxy compound is 1 mass part or more with respect to 100 mass parts of polyfunctional epoxy compounds, it exists in the tendency for the effect of reflow resistance to be fully acquired. Moreover, if it is 30 mass parts or less, the fall of curability and releasability and generation|occurrence|production of a molding defect will be suppressed, and there exists a tendency for handleability to improve.

In addition, from the viewpoint of curability and releasability, the content of the monofunctional epoxy compound is preferably from 0.05 parts by mass to 2 parts by mass, more preferably from 0.1 parts by mass to 100 parts by mass of the epoxy resin composition. 1 part by mass.

(B) Multifunctional epoxy compound

A polyfunctional epoxy compound has two or more epoxy groups in 1 molecule. Generally, a polyfunctional epoxy compound can be used for an epoxy resin composition, and the kind is not specifically limited as long as it has two or more epoxy groups in 1 molecule.

A polyfunctional epoxy compound may be an epoxy resin which has two or more epoxy groups in 1 molecule. Specifically, novolak-type epoxy resins (phenol novolak-type epoxy resins, o-cresol novolac-type epoxy resins, etc.) obtained by epoxidizing novolak resins, the novolak resins It is selected from phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene. At least one phenolic compound in the group composed of compounds is obtained by condensation or co-condensation with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; for making the phenolic compound, and benzaldehyde The triphenylmethane type phenolic resin obtained by condensation or co-condensation of aromatic aldehyde compounds such as willow aldehyde and so on under the acid catalyst is epoxidized, that is, triphenylmethane type epoxy resin; to make the phenolic compound and Co-condensation of naphthol compounds and aldehyde compounds under acidic catalysts to obtain novolac resins obtained by epoxidation, that is, copolymerized epoxy resins; as bisphenol A, bisphenol F, etc. Epoxy resins of the methyl methane type; Epoxy resins of the biphenyl type as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; Oxygen resins; epoxy resins containing sulfur atoms as diglycidyl ethers such as bisphenol S; epoxy resins as glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; as phthalates Formic acid, isophthalic acid, tetrahydrophthalic acid Glycidyl ester type epoxy resins of glycidyl esters of polycarboxylic acid compounds such as formic acid; active hydrogen bonded to nitrogen atoms such as glycidyl substituted aniline, diaminodiphenylmethane, isocyanuric acid, etc. The resultant is glycidylamine epoxy resin; the co-condensation resin of dicyclopentadiene and phenolic compound is epoxidized, which is dicyclopentadiene epoxy resin; the olefin bond in the molecule is epoxidized The resulting ones are vinyl cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy )cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; p-xylene as glycidyl ether of p-xylene modified phenol resin Modified epoxy resin; m-xylene modified epoxy resin as glycidyl ether of m-xylene modified phenol resin; terpene modified epoxy resin as glycidyl ether of terpene modified phenol resin; Dicyclopentadiene-modified epoxy resin of glycidyl ether of cyclopentadiene-modified phenol resin; cyclopentadiene-modified epoxy resin of glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resins of glycidyl ethers of ring-aromatic ring-modified phenol resins; naphthalene-type epoxy resins as glycidyl ethers of phenol resins containing naphthalene rings; halogenated phenol novolac-type epoxy resins; Hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; p-phenol aralkyl resins, naphthols Aralkyl-type phenolic resins such as aralkyl resins are epoxidized, that is, aralkyl-type epoxy resins and the like. Furthermore, epoxy resins such as epoxy resins such as silicone resin epoxides and acrylic resins are also exemplified. These epoxy resins may be used alone or in combination of two or more.

Among the above-mentioned epoxy resins, from the viewpoint of balance between reflow resistance and fluidity In other words, it is preferably selected from biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolak type epoxy resin, dicyclopentadiene Epoxy resins in the group consisting of olefinic epoxy resins, triphenylmethane epoxy resins, copolymer epoxy resins, and aralkyl epoxy resins (these are referred to as "specific epoxy resins") "). Specific epoxy resins may be used alone or in combination of two or more.

When the polyfunctional epoxy compound contains a specific epoxy resin, its content is preferably at least 30% by mass of the entire polyfunctional epoxy compound, more preferably 50% by mass, from the viewpoint of exhibiting the performance of the specific epoxy resin. Mass% or more.

From the viewpoint of fluidity, among the specific epoxy resins, biphenyl type epoxy resins, toluene type epoxy resins, diphenylmethane type epoxy resins or sulfur atom-containing epoxy resins are more preferable. From the viewpoint of properties, dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, or aralkyl-type epoxy resins are preferable. Specific examples of preferable epoxy resins are shown below.

The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable. In the epoxy resin represented by the following general formula (II), the position where the oxygen atom is substituted in R ⁸ is set as the 4 and 4' positions, the 3,3', 5,5' positions are methyl groups and YX-4000H (Mitsubishi Chemical Co., Ltd., trade name) in which R ⁸ is a hydrogen atom, and 4,4'-bis(2,3-epoxypropoxy)biphenyl in which all R ⁸ are hydrogen atoms , when all R ⁸ is a hydrogen atom and the position to be substituted by an oxygen atom in R ⁸ is set to 4 and 4', when the 3,3', 5,5' positions are methyl and other R ⁸ In the case of a hydrogen atom, YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixed product, is available as a commercial product.

In formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbons, or an aromatic group having 4 to 18 carbons, which may be the same or different. n is an average value and represents a number from 0 to 10.

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable. In the epoxy resin represented by the following general formula (III), the position where the oxygen atom is substituted in ^R9 is set as the 4-position and the 4'-position, when the 3,3', 5, and 5'-positions are methyl groups and except In addition to the case where R ⁹ is a hydrogen atom, R ¹⁰ is both a hydrogen atom, and 3 of the 3, 3', 5, and 5' positions in R ⁹ are methyl groups, and 1 is a tertiary butyl group, and other ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixture in the case where R ⁹ is a hydrogen atom and R ¹⁰ is both a hydrogen atom, can be obtained as a commercial product.

In formula (III), R ⁹ and R ¹⁰ represent a hydrogen atom or a monovalent organic group with 1 to 18 carbons, and they may be the same or different. n is an average value and represents a number from 0 to 10.

The diphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. In the epoxy resin represented by the following general formula (IV), R ¹¹ is a hydrogen atom, and the position to be substituted by an oxygen atom in R ¹² is 3, 3', 5, 5' when the 4-position and 4'-position are set YSLV-80XY (Nippon Steel & Sumikin Chemicals Co., Ltd., trade name) whose position is a methyl group and whose R ¹² is a hydrogen atom is available as a commercial item.

In formula (IV), R ¹¹ and R ¹² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and may be the same or different. n is an average value and represents a number from 0 to 10.

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, the epoxy resin represented by following general formula (V) is mentioned. In the epoxy resin represented by the following general formula (V), the position where the oxygen atom is substituted in R ¹³ is set to the 4th and 4' positions, the 3,3' positions are tertiary butyl, and the 6,6' positions YSLV-120TE (Nippon Steel & Sumikin Chemicals Co., Ltd., trade name) which is a methyl group and R ¹³ other than that is a hydrogen atom is available as a commercial item.

In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. n is an average value and represents a number from 0 to 10.

The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak-type phenol resin. For example, an epoxy resin obtained by epoxidizing novolac type phenol resins such as phenol novolak resin, cresol novolac resin, naphthol novolak resin, etc. by using methods such as glycidyl etherification is preferable, and the following general An epoxy resin represented by formula (VI). In the epoxy resin represented by the following general formula (VI), R ¹⁴ is a hydrogen atom, R ¹⁵ is a methyl group, ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd., trade name) and the like with i=1 It can be acquired as a commercial item.

In the formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number from 0 to 10.

The dicyclopentadiene-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (DIC Co., Ltd., brand name) where i=0 is available as a commercial item.

In formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number from 0 to 10.

The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin made of a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin such as a novolak-type phenol resin having a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and more preferably the following The epoxy resin represented by the general formula (VIII). Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Co., Ltd., trade name) in which i is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name), etc. It can be acquired as a commercial item.

In formula (VIII), R ¹⁷ and R ¹⁸ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i each independently represent an integer of 0 to 3, and k each independently represent an integer of 0 to 4. n is an average value and represents a number from 0 to 10.

The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound should be an epoxy resin that uses a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. , there is no special limitation. For example, an epoxy resin obtained by glycidyl etherification of a novolac-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and a ring represented by the following general formula (IX) is more preferable. oxygen resin. Among the epoxy resins represented by the following general formula (IX), R ²¹ is a methyl group and i is 1, j is 0, and k is NC-7300 (Nippon Kayaku Co., Ltd., trade name) and the like can be used as obtained from commercially available products.

In the formula (IX), R ¹⁹ to R ²¹ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i each independently represent an integer of 0 to 3, j each independently represent an integer of 0 to 2, and k each independently represent an integer of 0 to 4. l and m are average values, which are numbers from 0 to 10, and (l+m) means numbers from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is any one of following formula (IX-1) or formula (IX-2). In formula (IX-1) and formula (IX-2), the definition of i, j and k in R ¹⁹ ~ R ²¹ and the definition of i, j and k in formula (IX) in R ¹⁹ ~ R ²¹ same. n is 1 (when bonding via a methylene group) or 0 (when not bonding via a methylene group).

Examples of the epoxy resin represented by the general formula (IX) include random copolymers containing one structural unit and m structural units at random, and those containing one structural unit and m structural units alternately. Alternating copolymers, copolymers regularly containing one structural unit and m structural units, block copolymers containing one structural unit and m structural units in blocks, and the like. Any one of these may be used alone, or two or more of them may be used in combination.

As long as the aralkyl type epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and The epoxy resin used as a raw material from toluene, bis(methoxymethyl)biphenyl, or a phenol resin synthesized from these derivatives is not particularly limited. For example, it is preferable to combine dimethoxy-p-xylene, bis(toluene, Oxymethyl)biphenyl or the epoxy resin obtained by glycidyl etherification of the phenol resin synthesized by these derivatives, more preferably the ring represented by the following general formula (X) and general formula (XI) oxygen resin.

In the epoxy resin represented by the following general formula (X), i is 0 and ^R38 is NC-3000S (Nippon Kayaku Co., Ltd., trade name) of a hydrogen atom, and i is 0 at a mass ratio of 80:20 And R ³⁸ is the epoxy resin of hydrogen atom and all R ⁸ of general formula (II) are the epoxy resin of hydrogen atom mixed and formed CER-3000 (Nippon Kayaku Co., Ltd., trade name), etc. can be used as the market Acquired by sale. In addition, among the epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel Sumikin Chemical Co., Ltd., trade name) in which i is 0, j is 0, and k is 0 can be commercially available as goods obtained.

In formula (X) and formula (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ³⁷ , R ³⁹ to R ⁴¹ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i each independently represent an integer of 0 to 3, j each independently represent an integer of 0 to 2, k each independently represent an integer of 0 to 4, and l each independently represent an integer of 0 to 6. n is an average value, and each independently represents a number of 0 to 10.

Regarding R ⁸ ~ R ²¹ and R ³⁷ ~ R ⁴¹ in the general formula (II) ~ general formula (XI), the so-called "can be the same or different" refers to the 8 ~ 88 R ⁸ may all be the same or different. Regarding other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ , it means that the respective numbers contained in the formula may be the same or different. In addition, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different. For example, R ⁹ and R ¹⁰ may both be the same or different.

In addition, the organic group having 1 to 18 carbon atoms in general formula (III) to general formula (XI) is preferably an alkyl group or an aryl group.

The n in the general formula (II) to general formula (XI) is an average value, preferably in the range of 0 to 10 independently. If n is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the epoxy resin composition will decrease during melt molding, thereby suppressing occurrence of filling defects and deformation of bonding wires (metal wires connecting components and leads), etc. Propensity. It is more preferable that n is set to the range of 0-4.

Above, according to the general formula (II)~general formula (XI), the specific examples of the preferred multifunctional epoxy compounds that can be used in the epoxy resin composition have been described, as a more specific preferred multifunctional epoxy compound Epoxy compounds, from the viewpoint of reflow resistance, include 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl , from the viewpoint of formability and heat resistance, 4,4'-bis(2,3-epoxypropoxy)-biphenyl is exemplified.

In addition, in addition to the above, from the viewpoint of low warpage, it is also preferable to use a dihydroanthracene-type epoxy which is a diglycidyl ether of anthracenes substituted with an alkyl group or substituted with an aromatic ring or unsubstituted. Resin (for example, manufactured by Mitsubishi Chemical Co., Ltd., trade name: YX-8800), in terms of the balance between reflow resistance, curability and fluidity, is relatively Preferably, a methoxynaphthalene type epoxy resin (for example, manufactured by DIC Corporation, trade name HP-5000) is used.

The epoxy equivalent of the polyfunctional epoxy compound is not particularly limited. From the viewpoint of the balance of various properties such as formability, reflow resistance, and electrical reliability, the epoxy equivalent of the polyfunctional epoxy compound is preferably 100g/eq~1000g/eq, more preferably 150g/eq~500g/eq eq.

The softening point or melting point of the polyfunctional epoxy compound is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably 40°C to 180°C, and more preferably 50°C to 130°C from the viewpoint of workability at the time of preparation of the epoxy resin composition.

(C) Hardener

Generally speaking, the hardener can be used in the epoxy resin composition without any special limitation.

Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. Among them, at least one selected from the group consisting of phenol hardeners, amine hardeners, and acid anhydride hardeners is preferred, and phenol hardeners are more preferred.

As a phenol hardening agent, the phenol resin and polyhydric phenol compound which have two or more phenolic hydroxyl groups in 1 molecule are mentioned, for example. Specifically, polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; , resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenol compounds and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene At least one phenolic compound in the group, together with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicaldehyde Novolak-type phenolic resin obtained by condensation or co-condensation under an acidic catalyst; phenol aralkyl compound synthesized from the phenolic compound and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. Resins, naphthol aralkyl resins and other aralkyl type phenol resins; p-xylene and/or m-xylene modified phenol resins; melamine modified phenol resins; terpene modified phenol resins; Dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization of dicyclopentadiene; cyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin; Benzene-type phenol resin; triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicaldehyde under an acidic catalyst; co-condensing two or more of these Polymerized phenolic resins, etc. These phenolic curing agents may be used alone or in combination of two or more.

Among the phenolic hardeners, from the viewpoint of reflow resistance, it is preferred to be selected from the group consisting of aralkyl type phenol resins, dicyclopentadiene type phenol resins, triphenylmethane type phenol resins, benzaldehyde type phenol resins and At least one of the group consisting of a copolymerized phenol resin of an aralkyl type phenol resin and a novolac type phenol resin (these are referred to as "specific phenol hardeners"). The specific phenol hardener may be used alone or in combination of two or more.

When the curing agent contains a specific phenol curing agent, the content of the specific phenol curing agent is preferably at least 30% by mass of the entire curing agent, more preferably 50% by mass, from the viewpoint of fully exhibiting these performances. above

Examples of aralkyl-type phenol resins include phenol aralkyl resins and naphthol aralkyl resins synthesized from phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. . Aralkyl-type phenolic resins can also be further copolymerized with other phenolic resins. Examples of the aralkyl-type phenol resin to be copolymerized include: a copolymerization-type phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin, a copolymerization-type phenol resin of a salylaldehyde-type phenol resin and an aralkyl-type phenol resin. Copolymerized phenolic resins such as resins, novolak-type phenolic resins and aralkyl-type phenolic resins, etc.

Aralkyl-type phenolic resins as long as they are derived from at least one selected from the group consisting of phenol compounds and naphthol compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or these The phenolic resin to be synthesized is not particularly limited. For example, phenol resins represented by the following general formulas (XII) to (XIV) are preferable.

In formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group with 1 to 18 carbons, which may be the same or different. R ²² , R ²⁴ , R ²⁵ and R ²⁸ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R ²⁶ and R ²⁷ represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i are each independently an integer of 0 to 3, j are each independently an integer of 0 to 2, k are each independently an integer of 0 to 4, and p are each independently an integer of 0 to 4. n is an average value, and each independently represents a number of 0 to 10.

Among the phenol resins represented by the general formula (XII), MEH-7851 (Meiwa Chemical Co., Ltd., trade name) in which i is 0 and R ²³ is hydrogen atoms is available as a commercial product.

Among the phenolic resins represented by the general formula (XIII), i is 0 and k is 0 XL-225, XLC (Mitsui Chemicals Co., Ltd., trade name), MEH-7800 (Minghe Chemical Co., Ltd., trade name ) and the like are available as commercially available items.

Among the phenolic resins represented by the general formula (XIV), j is 0, k is 0 and p is 0 SN-170 (Nippon Steel Sumikin Chemical Co., Ltd., trade name), j is 0, k is 1 , SN-395 (Nippon Steel & Sumikin Chemicals Co., Ltd., trade name) in which R ²⁷ is a hydroxyl group and p is 0 can be obtained as commercial items.

The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (Shin Nippon Petrochemical Co., Ltd., brand name) in which i is 0 is available as a commercial item.

In formula (XV), R ²⁹ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number from 0 to 10.

The triphenylmethane-type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferable.

Among the phenol resins represented by the following general formula (XVI), MEH-7500 (Meiwa Chemical Co., Ltd., brand name) in which i is 0 and k is 0 can be obtained as a commercial item.

In the formula (XVI), R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i are each independently an integer of 0 to 3, and k are each independently an integer of 0 to 4. n is the average value, which is a number from 0 to 10.

The copolymerization type phenol resin of benzaldehyde type phenol resin and aralkyl type phenol resin is a copolymerization type phenol resin of phenol resin and aralkyl type phenol resin obtained by using a compound having a benzaldehyde skeleton as a raw material, and No particular limitation. For example, a phenol resin represented by the following general formula (XVII) is preferable.

Among the phenolic resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., trade name) in which i is 0, k is 0, and q is 0 is commercially available. goods obtained.

In formula (XVII), R ³² to R ³⁴ represent monovalent organic groups with 1 to 18 carbon atoms, and may be the same or different. i is an integer of 0 to 3 each independently, k is an integer of 0 to 4 each independently, and q is an integer of 0 to 5 each independently. l and m are average values, respectively, and each independently represents a number of 0 to 11. Wherein, the sum of l and m is a number from 1 to 11.

Novolak-type phenolic resins are not particularly phenolic resins as long as they are obtained by condensing or cocondensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. limited. For example, a phenol resin represented by the following general formula (XVIII) is preferable.

Among the phenolic resins represented by the following general formula (XVIII), i is 0 and R ³⁵ are all hydrogen atoms, Tamanol (Tamanol) 758, 759 (Arakawa Chemical Industry Co., Ltd., trade name), HP-850N ( Hitachi Chemical Co., Ltd., trade name) and the like are available as commercial items.

In formula (XVIII), R ³⁵ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ³⁶ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number from 0 to 10.

The "may be the same or different" described in the general formula (XII)~R ²² ~R ³⁶ in the general formula (XVIII), for example, means that the i R ²² in the formula (XII) can be the same or can be different from each other. Regarding other R ²³ to R ³⁶ , it means that the respective numbers contained in the formula may be the same or different from each other. In addition, R ²² to R ³⁶ may be the same or different. For example, ^R22 and ^R23 may be both the same or different, and ^R30 and ^R31 may be both the same or different.

The n in the general formula (XII)~general formula (XVIII) is preferably in the range of 0~10. If it is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the epoxy resin composition during melt molding will also be low, filling failure will not occur, and bonding wires (metal wires connecting elements and leads) will hardly occur. Deformation etc. It is preferable to set the average n in 1 molecule to the range of 0-4.

The functional group equivalent (hydroxyl equivalent in the case of a phenolic curing agent) of the hardener is not particularly limited. From the viewpoint of the balance of various properties such as formability, reflow resistance, and electrical reliability, it is preferably 70 g/eq to 1000 g/eq, and more preferably 80 g/eq to 500 g/eq.

The softening point or melting point of the hardener is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably 40°C to 180°C, and more preferably 50°C to 130°C from the viewpoint of workability during production of the epoxy resin composition.

(A) monofunctional epoxy compound and (B) synthesis of polyfunctional epoxy compound The ratio of the number of equivalents to the number of equivalents of (C) hardener, that is, the ratio of the number of functional groups in the hardener to the number of epoxy groups in monofunctional epoxy compounds and polyfunctional epoxy compounds (the number of functional groups in the hardener / The number of epoxy groups in the monofunctional epoxy compound and the polyfunctional epoxy compound) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small amount, it is preferable to set it as the range of 0.5-2.0, and it is more preferable to set it as the range of 0.6-1.3. From the viewpoint of formability and reflow resistance, it is more preferably in the range of 0.8 to 1.2.

(D) hardening accelerator

The epoxy resin composition may also contain a hardening accelerator. As a hardening accelerator, it can be generally used for an epoxy resin composition, and it does not specifically limit. Specifically, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 5,6- Cyclic amidine compounds such as dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene; add maleic anhydride, 1,4-benzoquinone, 2 ,5-Methylbenzoquinone, 1,4-Naphthoquinone, 2,3-Dimethylbenzoquinone, 2,6-Dimethylbenzoquinone, 2,3-Dimethoxy-5-methyl-1,4 -Quinone compounds such as -benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc., compounds with π bonds such as diazophenylmethane, phenol resin, etc. Compounds with intramolecular polarization; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of these tertiary amine compounds substances; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazole compounds; derivatives of these imidazole compounds; tributylphosphine, methyl Organic phosphine compounds such as diphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, phenylphosphine; add maleic anhydride, the quinone to these organic phosphine compounds compound, diazo Phosphorus compounds with intramolecular polarization formed from compounds with π bonds such as phenylmethane and phenol resin; tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium ethyl triphenyl borate, tetrabutylphosphonium Four-substituted phosphonium such as tetrabutyl borate. Four substituted borates; 2-ethyl-4-methylimidazole. Tetraphenylborate, N-methylmorpholine. Tetraphenyl borate and other tetraphenyl boron salts; these four-substituted phosphonium. Derivatives of tetrasubstituted borate and tetraphenylboron salt, etc. These curing accelerators may be used alone or in combination of two or more.

Among them, the hardening accelerator is preferably an adduct of a third phosphine compound and a quinone compound, more preferably an adduct of triphenylphosphine and benzoquinone or tributylphosphine from the viewpoint of hardening properties and fluidity. Adducts with benzoquinone. From the viewpoint of storage stability, an adduct of a cyclic amidine compound and a phenol resin is preferable, and a novolak-type phenol resin salt of diazabicycloundecene is more preferable. The content of the hardening accelerators exemplified above is preferably at least 60% by mass, more preferably at least 80% by mass, based on the total amount of hardening accelerators.

When using an adduct of a third phosphine compound and a quinone compound as a hardening accelerator, the total content of the adduct of a third phosphine compound and a quinone compound is preferably 60% by mass or more in the total amount of the hardening accelerator , more preferably more than 80% by mass.

The third phosphine used in the adduct of the third phosphine compound and the quinone compound is not particularly limited. Specifically, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(4-methylphenyl)phosphine, (4-Ethylphenyl)phosphine, Tris(4-propylphenyl)phosphine, Tris(4-butylphenyl)phosphine, Tris(isopropylphenyl)phosphine, Tris(tert-butylphenyl)phosphine ) phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2 , 6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, etc. phosphine. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

In addition, the quinone compound used in the adduct of the third phosphine compound and the quinone compound is not particularly limited. Specifically, o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, etc. are mentioned. From the viewpoint of moisture resistance or storage stability, p-benzoquinone is preferred.

The content of the hardening accelerator is not particularly limited as long as it is an amount that can achieve the hardening accelerating effect, and the total amount of (A) monofunctional epoxy compound, (B) polyfunctional epoxy compound, and (C) hardener ( Hereinafter, it is also called "resin component") 100 mass parts, Preferably it is 0.1 mass part - 10 mass parts, More preferably, it is 0.3 mass part - 5 mass parts. When it is 0.1 mass part or more, it exists in the tendency which can shorten time. Moreover, if it is 10 mass parts or less, it exists in the tendency which can suppress a hardening rate from being too fast, and can obtain a more favorable molded article.

(E) Inorganic filler

The epoxy resin composition may also contain an inorganic filler. Especially when using an epoxy resin composition as a sealing material of a semiconductor package, it is preferable to contain an inorganic filler.

The type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide , zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers having a flame retardant effect can also be used. Examples of inorganic fillers having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, magnesium and Composite metal hydroxides such as zinc composite hydroxides, zinc borate, and the like. Among them, fused silica is preferable from the viewpoint of decreasing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, and may use it in combination of 2 or more types. Examples of the state of the inorganic filler include powder, particles obtained by spheroidizing powder, fibers, and the like.

The average particle size of the inorganic filler is not particularly limited. Among them, from the viewpoint of formability, it is preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm. In addition, the average particle diameter of an inorganic filler is measured as a volume average particle diameter using the particle size distribution measuring apparatus of a laser diffraction scattering method.

The volume average particle diameter of the inorganic filler in an epoxy resin composition or its cured product can be measured by a well-known method. For example, the inorganic filler is extracted from the epoxy resin composition or cured product using an organic solvent, nitric acid, aqua regia, etc., and sufficiently dispersed by an ultrasonic disperser to prepare a dispersion liquid. Using this dispersion liquid, the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured by a laser diffraction scattering particle size distribution measuring device. Alternatively, the cured product may be embedded in a transparent epoxy resin, etc., and ground to obtain a cross-section, and the volume-average particle size distribution of the inorganic filler may be measured from the volume-based particle size distribution obtained by observing the obtained cross-section with a scanning electron microscope. particle size. Furthermore, measurement can also be performed by continuously performing two-dimensional cross-sectional observation of the cured product using a FIB device (focused ion beam SEM) or the like, and performing three-dimensional structure analysis.

From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is more spherical than angular, and the particle size distribution of the inorganic filler is preferable Distributed over a wide range.

From the viewpoint of low warpage of the epoxy resin composition, one having a large coefficient of linear expansion is preferable. For example, when the inorganic filler in the epoxy resin composition is silica, crystalline silica is better than fused silica.

In addition, the specific surface area of the inorganic filler is not particularly limited. Among them, from the viewpoint of formability and strength, it is preferably 0.5 m ² /g to 12 m ² /g, more preferably 1 m ² /g to 5 m ² /g. In addition, the specific surface area of an inorganic filler can be measured based on the nitrogen adsorption energy at 77K based on JIS Z 8830:2013.

The content of the inorganic filler is not particularly limited, but it is preferably 70% by mass in the epoxy resin composition from the viewpoint of improving flame retardancy, moldability, hygroscopicity, and strength, and reducing the coefficient of linear expansion. ~95% by mass, more preferably 85% by mass to 95% by mass from the viewpoint of improvement in hygroscopicity and reduction in coefficient of linear expansion. When the content rate of an inorganic filler is 70 mass % or more, there exists a tendency for flame retardancy and reflow resistance to improve. Moreover, when it is 95 mass % or less, it exists in the tendency for fluidity to be excellent. In addition, the content of the inorganic filler is preferably 70% by volume to 95% by volume, more preferably 75% by volume to 95% by volume, and still more preferably 80% by volume to 90% by volume relative to the total volume of the epoxy resin composition. %. When the content rate of an inorganic filler is 70 volume% or more, there exists a tendency for flame retardancy and reflow resistance to improve. Moreover, when it is 95 volume% or less, it exists in the tendency for fluidity to be excellent.

[Various additives]

In addition to the above-mentioned components, the epoxy resin composition may also contain coupling agents, ion exchangers, adhesion accelerators, mold release agents, flame retardants, colorants, thermal Various additives such as plastic resins and stress relieving agents. In addition to the additives exemplified below, the epoxy resin composition may contain various additives well known in the technical field as needed.

(coupling agent)

When the epoxy resin composition contains an inorganic filler, in order to improve the adhesiveness of a resin component and an inorganic filler, you may contain a coupling agent. Examples of coupling agents include: epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane and other silane compounds, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds and other known coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination.

Among them, the coupling agent preferably includes a silane coupling agent. The types and numbers of the alkoxysilyl group in the silane coupling agent and the organic functional groups other than the alkoxysilyl group can be selected as needed.

When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass relative to 100 parts by mass of the inorganic filler. When content of a coupling agent is 0.05 mass parts or more with respect to 100 mass parts of inorganic fillers, it exists in the tendency for the adhesiveness with a frame to improve further. When content of a coupling agent is 5 mass parts or less with respect to 100 mass parts of inorganic fillers, it exists in the tendency for the formability of a package to improve further.

(ion exchanger)

The epoxy resin composition may also contain an ion exchanger. Especially in the case of using the epoxy resin composition as a molding material for sealing, it is possible to improve the From the viewpoint of the moisture resistance and high-temperature storage characteristics of the electronic component device, an ion exchanger may be contained if necessary. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, and the like are exemplified. An ion exchanger may be used individually by 1 type, and may use it in combination of 2 or more types. 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 epoxy resin composition contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to capture halogen ion plasma. For example, with respect to 100 mass parts of resin components, Preferably it is 0.1 mass part - 30 mass parts, More preferably, it is 1 mass part - 5 mass parts.

(followed by accelerator)

From the viewpoint of further improving adhesiveness, the epoxy resin composition may contain an adhesion accelerator as needed. Specifically, derivatives of imidazole, triazole, tetrazole, triazine, etc., anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline, etc. And these derivatives, aliphatic acid amide compounds, dithiamine formate, thiadiazole derivatives, etc. These adhesion accelerators may be used alone or in combination of two or more.

(release agent)

The epoxy resin composition may contain a mold release agent from the viewpoint of obtaining good releasability from a mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, palm wax, higher fatty acids such as behenic acid and stearic acid, higher fatty acid metal salts, ester waxes such as behenic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. wait. A mold release agent may be used individually by 1 type, and may use it in combination of 2 or more types.

When the epoxy resin composition contains a release agent, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin component. When content of a mold release agent is 0.01 mass parts or more with respect to 100 mass parts of resin components, it exists in the tendency for sufficient mold release property to be acquired. There exists a tendency for better adhesiveness to be acquired as it is 10 mass parts or less.

(flame retardant)

From the viewpoint of improving the flame retardancy of the composition, the epoxy resin composition may contain a conventionally known flame retardant if necessary. Specifically, brominated epoxy resins; inorganic substances such as antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, and zinc oxide; red phosphorus coated with thermosetting resins such as phenol resins; phosphoric acid esters, etc. Phosphorus compounds; nitrogen-containing compounds such as melamine, melamine derivatives, melamine-modified phenol resins, compounds with triazine rings, cyanuric acid derivatives, and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene compound; the composite metal hydroxide shown in the following composition formula (II), etc.

p(M1 _a O _b ). q(M2 _c O _d ). m(H ₂ O)...Formula (II)

In formula (II), M1 and M2 represent mutually different metal elements, and a, b, c, d, p, q, and m represent positive numbers.

M1 and M2 in the formula (II) are not particularly limited as long as they are different metal elements. From the viewpoint of flame retardancy, M1 is preferably selected from metal elements of the third period, alkaline earth metal elements of Group IIA, and metal elements belonging to Group IVB, Group IIB, Group VIII, Group IB, Group IIIA, and Group IVA. , and M2 is selected from the transition metal elements of Group IIIB~IIB, more preferably M1 is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M2 is selected from iron, cobalt, nickel, copper and zinc. In addition, from the viewpoint of fluidity, it is preferable that M1 is magnesium and M2 is zinc or nickel. The ratio of p to q (p/q) is not particularly limited, and is preferably 1/99˜1/1. Furthermore, the classification of metal elements is based on the long-period periodic law table in which typical elements are set as subgroup A and transition elements are set as subgroup B (source: "Chemical Encyclopedia 4" issued by Kyoritsu Publishing Co., Ltd., 1987 On February 15, 2009, the 30th brush of the miniature version) will be carried out.

Examples of other flame retardants include compounds containing metal elements such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and iron dicyclopentadienyl. These flame retardants may be used alone or in combination of two or more.

When the epoxy resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. Especially, with respect to 100 mass parts of (A) epoxy resins, Preferably it is 1 mass part - 30 mass parts, More preferably, it is 2 mass parts - 15 mass parts.

(Colorant)

The epoxy resin composition may further contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. A coloring agent may be used individually by 1 type, and may use it in combination of 2 or more types.

(thermoplastic resin)

The epoxy resin composition may contain thermoplastic resins such as indene oligomers, which are copolymer resins of polyphenylene ethers, indenes such as indene and alkylindene, styrenes such as styrene and alkylstyrene, and phenols, as needed. A thermoplastic resin may be used individually by 1 type, and may use it in combination of 2 or more types.

(stress reliever)

The epoxy resin composition may also contain stress relieving agents such as silicone oil and silicone rubber particles. By containing the stress relieving agent, the warping deformation of the package and the occurrence of package cracks can be further reduced. Examples of the stress relieving agent include generally known stress relieving agents (flexibility agents). Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based, and natural rubber (NR), acrylonitrile-butadiene rubber (NBR), acrylic rubber, urethane rubber, silicone powder and other rubber particles, methyl methacrylate-styrene-butadiene copolymer (MBS), Rubber particles having a core-shell structure such as methyl methacrylate-silicone copolymer and methyl methacrylate-butyl acrylate copolymer. The stress relieving agent may be used alone or in combination of two or more. Among them, silicone-based stress relieving agents are preferable. As a silicone-based stress reliever, it can be listed Examples include those having epoxy groups, those having amine groups, and those obtained by modifying these with polyether.

(Preparation Method of Epoxy Resin Composition)

The preparation method of the epoxy resin composition is not particularly limited. A general method includes a method in which various components are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder, or the like, followed by cooling and pulverization. More specifically, for example, the method of stirring and mixing the above-mentioned various components, kneading with a kneader, roll, extruder, etc. heated to 70° C. to 140° C. in advance, and cooling, smash.

The epoxy resin composition is preferably solid at normal temperature and normal pressure (eg, 25°C, atmospheric pressure). The shape of the epoxy resin composition when it is solid is not particularly limited, and examples thereof include powder, granular, and flake shapes. From the standpoint of handling, the size and mass of the epoxy resin composition in the form of a sheet are the same as the molding conditions of the package.

<Electronic component device of the first embodiment>

An electronic component device according to a first embodiment includes an element sealed with the epoxy resin composition.

Examples of electronic components include mounting elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, etc.) on lead frames, wiring, etc., using epoxy resin compositions. It is obtained by sealing the component parts obtained by carrying supporting members such as tapes, wiring boards, glass, silicon wafers, and organic substrates.

More specifically, can enumerate: Dual Inline Package (Dual Inline Package, DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead Package (Small Outline J -lead package, SOJ), Thin Small Outline Package (Thin Small Outline Package, TSOP), Thin Quad Flat Package (Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have the function of fixing components on the lead frame After connecting the terminal portion and the lead portion of components such as bonding pads with wire bonding and bumps, the epoxy resin composition is used to seal the structure by transfer molding, etc.; tape carrier package (Tape Carrier Package, TCP), It has a structure that uses epoxy resin composition to seal the components that are connected to the carrier tape with bumps; substrate flip-chip (Chip On Board, COB) modules, hybrid ICs, polycrystalline modules, etc., which have the use of ring The epoxy resin composition seals the components on the wiring formed on the support member by wire bonding, flip-chip bonding, solder, etc.; ball array (Ball Grid Array, BGA), chip size package (Chip Size Package) , CSP), multi-chip package (Multi Chip Package, MCP), etc., which have components mounted on the surface of a support member with terminals for wiring board connection formed on the back surface, and the components are formed on the support member by bumps or wire bonding. After the wiring is connected, the structure of the device is sealed with an epoxy resin composition. Moreover, an epoxy resin composition can also be used preferably for a printed wiring board.

As a method of sealing an electronic component device using an epoxy resin composition, a low-pressure transfer molding method, an injection molding method, a compression molding method, etc. are mentioned. Among these, low-pressure transfer injection molding is generally used.

<The curable resin composition of the second embodiment>

The curable resin composition of the second embodiment contains (A') a curable resin, (B') a curing agent, and (C') a compound having a (meth)acryl group. The curable resin composition may further contain other components as necessary. Hereinafter, (C') a compound having a (meth)acryloyl group may be referred to as a "specific acrylic compound".

When the curable resin composition contains the specific acrylic compound, a curable resin composition excellent in reflow resistance can be obtained. The reason for this is not necessarily clear, but it is speculated that the acrylic resin has no polar groups after the reaction and has low water absorption, so it is excellent in reflow resistance.

(C') specific acrylic compound

The curable resin composition contains a specific acrylic compound. The specific acrylic compound may be used alone or in combination of two or more. The specific acrylic compound is not particularly limited as long as it has a (meth)acryl group.

The number of (meth)acryloyl groups contained in the specific acrylic compound is not limited, but is preferably 1-10, more preferably 1-3, still more preferably 1 or 2. In this study, the specific acrylic compound preferably has a (meth)acryl group, more preferably has a (meth)acryloxy group. In this study, the specific acrylic compound preferably includes (meth)acrylate compound.

Specific examples of specific acrylic compounds include tricyclodecane dimethanol di(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, Polyethylene glycol #200 di(meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.

The specific acrylic compound can be solid or liquid at normal temperature (25° C.), preferably liquid.

The molecular weight of the specific acrylic compound is not particularly limited. From the viewpoint of fluidity and reflow resistance, it is preferably 180-320, more preferably 180-270, and still more preferably 190-220.

In one embodiment, the specific acrylic compound may have an alicyclic structure. The alicyclic structure may or may not contain unsaturated bonds. The alicyclic structure may have a substituent or may not have a substituent. For example, a specific acrylic compound may have a dicyclopentadiene skeleton.

In yet another embodiment, the specific acrylic compound may have an epoxy group. When a specific acrylic compound has an epoxy group, it exists in the tendency which can fully maintain curability.

When the specific acrylic compound has an epoxy group, the number of epoxy groups contained in the specific acrylic compound is not limited, but is preferably 1 from the viewpoint of reflow resistance.

Among them, the specific acrylic compound preferably has an alicyclic epoxy group from the viewpoints of reflow resistance, curability, and the like. When the specific acrylic compound has an alicyclic epoxy group, the alicyclic epoxy group is formed by bonding an oxygen atom to two adjacent carbon atoms constituting the cycloaliphatic skeleton. The number of carbon atoms in the cycloaliphatic skeleton of the alicyclic epoxy group is not particularly limited. The cyclic aliphatic skeleton is, for example, preferably a 5-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and still more preferably a 6-membered ring.

As an example of the specific acrylic compound which has an alicyclic epoxy group, the compound represented by following general formula (a) is mentioned.

[chem 24]

In the general formula (a), R ¹ represents a hydrogen atom or a methyl group. R ² represents a monovalent substituent. X represents a single bond or a divalent linking group. n represents an integer from 0 to 9.

R ¹ is preferably methyl.

The monovalent substituent represented by R ² is not particularly limited, and examples thereof include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. When a plurality of R ² exists, the plurality of R ² may be the same or different.

The divalent linking group in X is not particularly limited, and examples thereof include aliphatic hydrocarbon groups and the like. Examples of the aliphatic hydrocarbon group include linear or branched alkylene groups and the like. When X is an alkylene group, the number of carbons contained in the alkylene group is not particularly limited, but is preferably 1-10, more preferably 1-3, and still more preferably 1. The alkylene group may have an arbitrary substituent. In addition, the carbon number contained in the said alkylene group is set not including the carbon number contained in a branch or a substituent.

n is preferably 0-3, more preferably 0.

As an example of the specific acrylic compound having an alicyclic epoxy group represented by the general formula (a), a compound represented by the following formula (b) (3,4-epoxycyclohexylmethyl methacrylate ).

As the specific acrylic compound, synthesizers can be used, and commercially available ones can also be used. Taste. As a commercial item, 3, 4- epoxy cyclohexyl methyl methacrylate (brand name: Cyclomer (CYCLOMER) M100, the product made by Daicel Corporation) is mentioned.

The content of the specific acrylic compound is preferably from 1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, still more preferably from 5 to 20 parts by mass, particularly preferably 10 parts by mass to 20 parts by mass. When content of a specific acrylic compound is 1 mass part or more with respect to 100 mass parts of curable resins, it exists in the tendency which is excellent in fluidity, and can fully acquire the effect of reflow resistance. Moreover, if it is 30 mass parts or less, the fall of curability and releasability, and generation|occurrence|production of a molding defect can be suppressed, and there exists a tendency for workability to improve.

In addition, from the viewpoint of curability and releasability, the content of the specific acrylic compound is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the curable resin composition. share.

Whether or not a specific acrylic compound is contained in the curable resin composition can be confirmed, for example, by mass spectrometry of a solvent extract.

(A') Hardening resin

The curable resin composition contains a curable resin. The curable resin is not particularly limited, and may be thermosetting or photocurable. The curable resin is preferably thermosetting. The curable resin may be cured by self-polymerization or may be cured by reaction with a curing agent, a crosslinking agent, or the like.

The functional group that reacts to produce a curable resin is not particularly limited, and examples thereof include acyclic epoxy groups such as glycidyl groups, alicyclic epoxy groups, hydroxyl groups, carboxyl groups, amino groups, acryl groups, and isocyanate groups. In terms of the balance of the characteristics of the sealing material From a viewpoint, a curable resin containing a cyclic ether group is preferable, and a curable resin (epoxy resin) containing an epoxy group is more preferable.

When the curable resin is an epoxy resin, the type of the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. When the curable resin is an epoxy resin, the details of the epoxy resin are the same as those of the (B) polyfunctional epoxy compound of the first embodiment. Furthermore, in the description of (B) polyfunctional epoxy compound of the first embodiment, the description of "polyfunctional epoxy compound" is replaced by "epoxy resin", and the description of "epoxy resin composition" is replaced by "Curable resin composition".

The functional group equivalent of the curable resin is not particularly limited. From the viewpoint of the balance of various properties such as formability, reflow resistance, and electrical reliability, the functional group equivalent weight of the curable resin is preferably 100g/eq~1000g/eq, more preferably 150g/eq~500g/eq.

The softening point or melting point of the curable resin is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably from 40°C to 180°C, and from the viewpoint of workability during preparation of the curable resin composition, it is more preferably from 50°C to 130°C.

(B') Hardener

The curable resin composition contains a curing agent. The type of curing agent is not particularly limited, and can be selected according to the type of curable resin, desired properties of the curable resin composition, and the like.

Examples of the curing agent when the curable resin is an epoxy resin include those described as the curing agent in the first embodiment. Curing agent when the curable resin is epoxy resin Details are the same as those of the curing agent in the first embodiment.

In addition, description of "epoxy resin composition" in the description of the curing agent of the first embodiment is replaced with "curable resin composition".

In addition, in the description of the hardening agent of the first embodiment, the ratio of "the total equivalent number of (A) monofunctional epoxy compound and (B) polyfunctional epoxy compound to the equivalent number of (C) hardener", that is, the hardening The ratio of the number of functional groups in the agent to the number of epoxy groups in the monofunctional epoxy compound and the polyfunctional epoxy compound (the number of functional groups in the hardener/the number of epoxy groups in the monofunctional epoxy compound and the polyfunctional epoxy compound) " is replaced with "the equivalent ratio of curable resin to hardener, that is, the ratio of the functional groups in the hardener to the functional groups in the curable resin (functional group in the hardener/functional group in the curable resin) ".

(D') hardening accelerator

The curable resin composition may also contain a curing accelerator. Details of the hardening accelerator are the same as those of the hardening accelerator of the first embodiment.

In addition, description of "epoxy resin composition" in the description of the hardening accelerator of the first embodiment is replaced with "curable resin composition".

In addition, the "resin component" in the description of the content of the hardening accelerator in the first embodiment means "the total of the hardening resin and the hardening agent".

(E') Inorganic filler

The curable resin composition may also contain an inorganic filler. Details of the inorganic filler are the same as those of the inorganic filler of the first embodiment.

In addition, in the description of the inorganic filler of the first embodiment, "epoxy resin "Composition" is replaced with "curable resin composition".

[Various additives]

The curable resin composition may contain various additives such as coupling agents, ion exchangers, adhesion accelerators, mold release agents, flame retardants, colorants, thermoplastic resins, and stress relieving agents as exemplified below in addition to the above-mentioned components. Details of various additives are the same as those of the first embodiment.

In addition, description of "epoxy resin composition" in the description of various additives in the first embodiment is replaced with "curable resin composition".

(Method for preparing curable resin composition)

The method for preparing the curable resin composition is not particularly limited. Details of the production method of the curable resin composition are the same as those of the production method of the epoxy resin composition of the first embodiment. In addition, description of "epoxy resin composition" in the description of the production method of the epoxy resin composition of the first embodiment is replaced with "curable resin composition".

<Electronic component device of the second embodiment>

An electronic component device according to a second embodiment includes an element sealed with the curable resin composition. Details of the electronic component device are the same as those of the electronic component device of the first embodiment. In addition, description of "epoxy resin composition" in the description of the electronic component device of the first embodiment is replaced with "curable resin composition".

[Example]

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" as a quality benchmark.

[Example of the first embodiment]

(Example 1-1~Example 1-8, Comparative Example 1-1~Comparative Example 1-5)

The following components were formulated in the amounts (unit: parts by mass) shown in Table 1 and Table 2 below, and roll kneaded at a kneading temperature of 100°C and a kneading time of 10 minutes to prepare Examples 1- 1~Epoxy resin compositions of Examples 1-8 and Comparative Examples 1-1~Comparative Examples 1-5. Furthermore, a blank column in the table means "no deployment".

Examples of monofunctional epoxy compounds are used below.

． Epoxy compound 1: an epoxy compound represented by formula (c) having an epoxy group equivalent of 196 g/eq (manufactured by Daicel Co., Ltd., Cyclomer M100)

． Epoxy compound 2: 2-biphenyl glycidyl ether with an epoxy group equivalent weight of 226g/eq

The epoxy compounds used for comparison are as follows.

． Epoxy compound 3: a difunctional alicyclic epoxy compound having an epoxy group equivalent of 126 g/eq (manufactured by Daicel Co., Ltd., CELLOXIDE 2021)

The polyfunctional epoxy compound (the polyfunctional epoxy compound which has two or more epoxy groups in 1 molecule) was used as follows.

． Multifunctional epoxy compound 4: a methoxynaphthalene epoxy resin (manufactured by DIC Co., Ltd., HP-5000) with an epoxy group equivalent of 250 g/eq and a softening point of 58° C.

． Multifunctional epoxy compound 5: the phenol aralkyl type epoxy resin containing the extended biphenyl skeleton of 241g/eq and softening point of epoxy group equivalent (Nippon Kayaku Co., Ltd. Co., Ltd., CER-3000L)

． Multifunctional epoxy compound 6: an epoxy group equivalent of 282 g/eq and a softening point of 56° C. extended biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000)

As a hardening agent, a xylenol resin (manufactured by Meiwa Kasei Co., Ltd., MEHC-7800SS) having a hydroxyl equivalent of 175 g/eq and a softening point of 70° C. was used.

As the hardening accelerator, a betaine-type adduct of triphenylphosphine and p-benzoquinone was used.

As the inorganic filler, spherical fused silica with an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² /g was used.

As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane was used.

Other additives are palm wax and carbon black.

[Evaluation of epoxy resin composition]

The properties of the epoxy resin compositions prepared in Example 1-1 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-5 were evaluated by the following characteristic tests of (1) to (5). . The evaluation results are shown in Table 1 and Table 2 below. Furthermore, unless otherwise indicated, the molding of the epoxy resin composition was carried out by a transfer molding machine at a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. In addition, if necessary, post-curing is performed at 175° C. for 5 hours.

(1) Swirl

The epoxy resin composition was molded under the conditions described above using a mold for swirl measurement according to EMMI-1-66, and the flow distance (cm) was determined.

(2) Hardness when hot

The epoxy resin composition was molded into a circular plate with a diameter of 50mm x a thickness of 3mm under the above conditions, and immediately after the molding was performed using a Shore D-type hardness tester (manufactured by Uejima Seisakusho Co., Ltd., HD-1120 (D type)) Determination.

(3) Shear adhesion at 260°C

An epoxy resin composition was molded on a silver-plated copper plate under the above-mentioned conditions with a bottom surface diameter of 4 mm, an upper surface diameter of 3 mm, and a height of 4 mm, and post-cured under the above-mentioned conditions. Thereafter, using Series 4000 manufactured by Nordson Advanced Technology Co., Ltd., the temperature of the copper plate was kept at 260° C. and the shear adhesion force (MPa) was determined at a shear rate of 50 μm/s.

(4) Water absorption

The disc formed in (2) above was post-hardened under the conditions described above. Thereafter, the obtained disc was left to stand for 168 hours under the conditions of 85° C. and 60% RH, and the mass change before and after being left was measured. Based on the measurement results, the water absorption rate was calculated by the following formula.

Water absorption rate (mass%)={(the mass of the disc after placement-the mass of the disc before placement)/the mass of the disc before placement}×100

(5) Reflow resistance

80-pin flat package (QFP) with an external dimension of 20mm×14mm×2mm for mounting a silicon chip of 8mm×10mm×0.4mm (lead frame material: copper alloy, the upper surface of the chip pad and the silver-plated lead tip) , using the epoxy resin composition to carry out molding under the above-mentioned conditions, and to perform post-curing under the above-mentioned conditions. Will place The obtained package was humidified for 168 hours under conditions of 85° C. and 85% RH. Afterwards, the reflow process was performed at a temperature of 250°C, 260°C, or 270°C for 10 seconds, and the presence or absence of cracks on the outside of the package was visually observed, and an ultrasonic flaw detection device (manufactured by Hitachi Construction Machinery Co., Ltd. , HYE-FOCUS) to observe the presence or absence of peeling inside the package. The reflow resistance was evaluated as the sum of the number of packages in which cracks and peeling occurred with respect to the number of test packages (10).

As shown in Table 1 and Table 2, compared with Comparative Example 1-1 to Comparative Example 1-5 not containing a monofunctional epoxy compound, Example 1-1 to Example 1-1 containing a monofunctional epoxy compound Among 8, the reflow resistance at 260° C. or higher is excellent. In addition, the curability can also be maintained sufficiently.

In addition, in Example 1-1 to Example 1-5, the content of the monofunctional epoxy compound was 5 parts by mass to 20 parts by mass in Example 1-1 and Example 1-3 with respect to the polyfunctional epoxy compound. , Examples 1-4, and Examples 1-5 tended to exhibit excellent swirl flow and good fluidity.

[Example of the second embodiment]

(Example 2-1~Example 2-7, Comparative Example 2-1~Comparative Example 2-5)

The following components were prepared in the amounts (unit: parts by mass) shown in Table 3 and Table 4 below, and roll kneaded at a kneading temperature of 100°C and a kneading time of 10 minutes. refining, thereby preparing curable resin compositions of Example 2-1 to Example 2-7 and Comparative Example 2-1 to Comparative Example 2-5, respectively. Furthermore, a blank column in the table means "no allocation".

The specific acrylic compounds of the examples are used below.

． Specific acrylic compound 1: an epoxy compound represented by formula (b) having an epoxy group equivalent of 196 g/eq (manufactured by Daicel Co., Ltd., Cyclomer M100)

The compounds used for comparison are as follows.

． Compound 1 for comparison: a difunctional alicyclic epoxy compound having an epoxy group equivalent of 126 g/eq (manufactured by Daicel Co., Ltd., CELLOXIDE 2021; no (meth)acryl group)

Curable resin is used below.

． Epoxy resin 1: a methoxynaphthalene epoxy resin having an epoxy group equivalent of 250 g/eq and a softening point of 58° C. (manufactured by DIC Co., Ltd., HP-5000)

． Epoxy resin 2: a phenol aralkyl type epoxy resin having an extended biphenyl skeleton having an epoxy group equivalent of 241 g/eq and a softening point of 96° C. (manufactured by Nippon Kayaku Co., Ltd., CER-3000L)

． Epoxy resin 3: an epoxy group equivalent of 282 g/eq and a softening point of 56° C. extended biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000)

As a hardening agent, a xylenol resin (manufactured by Meiwa Kasei Co., Ltd., MEHC-7800SS) having a hydroxyl equivalent of 175 g/eq and a softening point of 70° C. was used.

As the hardening accelerator, a betaine-type adduct of triphenylphosphine and p-benzoquinone was used.

As the inorganic filler, spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² /g was used.

As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane was used.

Other additives are palm wax and carbon black.

[Evaluation of Curable Resin Composition]

The characteristics of the curable resin compositions prepared in Example 2-1 to Example 2-7 and Comparative Example 2-1 to Comparative Example 2-5 were evaluated by the following characteristic tests of (1) to (5). . The evaluation results are shown in Table 3 and Table 4 below. Furthermore, unless otherwise indicated, the molding of the curable resin composition was performed by a transfer molding machine at a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. In addition, if necessary, post-curing is performed at 175° C. for 5 hours.

(1) Swirl

The curable resin composition was molded under the above conditions using a mold for swirl flow measurement according to EMMI-1-66, and the flow distance (cm) was determined.

(2) Hardness when hot

The curable resin composition was molded into a circular plate with a diameter of 50 mm x a thickness of 3 mm under the above conditions, and immediately after the molding was performed using a Shore D-type hardness tester (manufactured by Uejima Seisakusho Co., Ltd., HD-1120 (D type)). Determination.

(3) Shear adhesion at 260°C

A curable resin composition was molded on a silver-plated copper plate under the above-mentioned conditions with a bottom diameter of 4 mm, an upper surface diameter of 3 mm, and a height of 4 mm, and post-cured under the above-mentioned conditions. The temperature of the copper plate was then maintained using a Series 4000 manufactured by Nordson Advanced Technology Inc. The shear adhesion force (MPa) was determined at 260° C. and at a shear rate of 50 μm/s.

(4) Water absorption

The disc formed in (2) above was post-hardened under the conditions described above. Thereafter, the obtained disc was left to stand for 168 hours under the conditions of 85° C. and 60% RH, and the mass change before and after being left was measured. Based on the measurement results, the water absorption rate was calculated by the following formula.

Water absorption rate (mass%)={(the mass of the disc after placement-the mass of the disc before placement)/the mass of the disc before placement}×100

(5) Reflow resistance

80-pin flat package (QFP) with an external dimension of 20mm×14mm×2mm for mounting a silicon chip of 8mm×10mm×0.4mm (lead frame material: copper alloy, the upper surface of the chip pad and the silver-plated lead tip) , Molding is performed under the above-mentioned conditions using a curable resin composition, and post-curing is performed under the above-mentioned conditions. The obtained package was humidified for 168 hours under conditions of 85° C. and 85% RH. Afterwards, the reflow process was performed at a temperature of 250°C, 260°C, or 270°C for 10 seconds, and the presence or absence of cracks on the outside of the package was visually observed, and an ultrasonic flaw detection device (manufactured by Hitachi Construction Machinery Co., Ltd. , HYE-FOCUS) to observe the presence or absence of peeling inside the package. The reflow resistance was evaluated as the sum of the number of packages in which cracks and peeling occurred with respect to the number of test packages (10).

As shown in Table 3 and Table 4, compared with Comparative Example 2-1 to Comparative Example 2-5 that did not contain a specific acrylic compound, in Examples 2-1 to 2-7 that contained a specific acrylic compound, especially Excellent reflow resistance above 260°C. In addition, you can also charge Maintain the hardness when hot.

In addition, in Example 2-1 to Example 2-5, the content of the specific acrylic compound is 5 mass parts to 20 mass parts with respect to the polyfunctional epoxy compound, Example 2-1, Example 2-3, and implementation Examples 2-4 and Examples 2-5 tended to exhibit excellent swirl flow and good fluidity.

The disclosures of Japanese Patent Application No. 2017-072118 filed on March 31, 2017 and Japanese Patent Application No. 2017-072119 filed on March 31, 2017 are incorporated in this specification by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if they were specifically and individually stated to be incorporated by reference The status of each document, patent application, and technical specification.

Claims (9)

An epoxy resin composition comprising: a monofunctional epoxy compound having one epoxy group in one molecule; a multifunctional epoxy compound having two or more epoxy groups in one molecule; and a hardener; The monofunctional epoxy compound includes a monofunctional epoxy compound represented by the following general formula (a) having one alicyclic epoxy group in one molecule, and the epoxy resin composition is at 25°C, Thermosetting compositions that are solid at atmospheric pressure;

In the general formula (a), R represents an alkyl group substituted with an ethylenically unsaturated double bond, and n represents an integer of 0-10. The epoxy resin composition as described in claim 1 of the patent application, in the general formula (a), R represents an alkyl group substituted with a (meth)acryloyl group. As the epoxy resin composition described in item 1 or item 2 of the scope of the patent application, the monofunctional epoxy compound comprises a compound represented by the following general formula (b),

In the general formula (b), R ¹ represents a hydrogen atom or a methyl group; R ² represents a monovalent substituent not containing an epoxy group; X represents a single bond or a divalent linking group; n represents an integer of 0-9. The epoxy resin composition as described in item 1 or item 2 of the scope of patent application, wherein the content of the monofunctional epoxy compound relative to 100 parts by mass of the polyfunctional epoxy compound is 1 mass part to 30 mass parts share. The epoxy resin composition as described in item 1 or item 2 of the scope of patent application, wherein relative to 100 parts by mass of the multifunctional epoxy resin composition, the content of the monofunctional epoxy compound is 10 parts by mass~ 20 parts by mass. The epoxy resin composition according to claim 1 or 2, which further contains a hardening accelerator. The epoxy resin composition according to claim 1 or 2, which further contains an inorganic filler, and the content of the inorganic filler is 70% relative to the total volume of the epoxy resin composition. Volume%~95vol%. The epoxy resin composition as described in claim 1 or claim 2, which further contains a silane coupling agent. An electronic component device comprising an element sealed with the epoxy resin composition described in any one of claims 1 to 8 of the patent application.