WO2018181384A1

WO2018181384A1 - Epoxy resin composition, curable resin composition and electronic component device

Info

Publication number: WO2018181384A1
Application number: PCT/JP2018/012551
Authority: WO
Inventors: 朱美山口; 貴広中田; 中村　真也; 大下　毅; 遠藤　由則
Original assignee: 日立化成株式会社
Priority date: 2017-03-31
Filing date: 2018-03-27
Publication date: 2018-10-04
Also published as: TWI824463B; MY198033A; JP2022101587A; TW201839023A; JP7416116B2; SG10202101445YA; JP7226306B2; SG11201908910VA; TW202229391A; TWI801371B; JPWO2018181384A1

Abstract

This epoxy resin composition contains: a monofunctional epoxy compound which has one epoxy group in each molecule; a polyfunctional epoxy compound which has two or more epoxy groups in each molecule; and a curing agent. This curable resin composition contains: a curable resin; a curing agent; and a compound having a (meth)acryloyl group. In addition, this electronic component device is provided with an element that is sealed by means of this epoxy resin composition or this curable resin composition.

Description

Epoxy resin composition, curable resin composition, and electronic component device

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

With recent downsizing, weight reduction, and higher performance of electronic devices, mounting density has been increasing. As a result, the mainstream of electronic component devices is changing from conventional pin insertion type packages to surface mount type packages such as IC (Integrated Circuit) and LSI (Large Scale Integration).

The surface mounting type package is different from the conventional pin insertion type. That is, when the pins are attached to the wiring board, the conventional pin insertion type package is soldered from the back surface of the wiring board after the pins are inserted into the wiring board, so that the package is not directly exposed to high temperature. However, in the surface mount type package, the entire electronic component device is processed by a solder bath, a reflow device or the like, so that the package is directly exposed to a soldering temperature (reflow temperature). As a result, when the package absorbs moisture, moisture due to moisture absorption rapidly expands during soldering, and the generated vapor pressure acts as a peeling stress, and peeling occurs between the insert of the element, lead frame, etc., and the sealing material. This may cause package cracks, poor electrical characteristics, and the like. For this reason, it is desired to develop a sealing material that is excellent in adhesiveness to the insert, and thus excellent in solder heat resistance (reflow resistance).

In order to meet the above requirements, various studies have been made on the epoxy resin as the main material from the viewpoint of reducing moisture absorption. Further, from the viewpoint of improving the adhesion with an insert such as an element lead frame, the use of a silane coupling agent is being studied as a modifier for the inorganic filler contained in the sealing material. Specifically, use of an epoxy group-containing silane coupling agent or amino group-containing silane coupling agent (for example, see Patent Document 1), use of a sulfur atom-containing silane coupling agent (for example, see Patent Document 2), etc. It is being considered.

JP-A-11-147939 JP 2000-103940 A

However, the present situation is that a curable resin composition that sufficiently satisfies the reflow resistance practically has not been obtained.

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

Means for solving the above problems include the following first embodiment.
<1> An epoxy resin composition containing a monofunctional epoxy compound having one epoxy group in one molecule, a polyfunctional epoxy compound having two or more epoxy groups in one molecule, and a curing agent.
<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 a 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 with respect to 100 parts by mass of the polyfunctional epoxy compound is 1 part by mass to 30 parts by mass.
<5> The epoxy resin composition according to any one of <1> to <4>, further containing a curing accelerator.
<6> Any one of <1> to <5>, further comprising an inorganic filler, wherein the content of the inorganic filler is 70% by volume to 95% by volume with respect to the total volume of the epoxy resin composition 2. The epoxy resin composition according to item 1.
<7> The epoxy resin composition according to any one of <1> to <6>, further containing a silane coupling agent.
<8> An electronic component device comprising an element sealed with the epoxy resin composition according to any one of <1> to <7>.

Furthermore, means for solving the above-described problems include the following second embodiment.
<9> A curable resin composition containing a curable resin, a curing agent, and a compound having a (meth) acryloyl group.
<10> The curable resin composition according to <9>, wherein the compound having a (meth) acryloyl group has a molecular weight of 180 to 320.
<11> The curable resin composition according to <9> or <10>, wherein the compound having a (meth) acryloyl group includes a (meth) acrylic acid ester compound.
<12> The curable resin composition according to any one of <9> to <11>, wherein the compound having a (meth) acryloyl group has an alicyclic structure.
<13> The curable resin composition according to any one of <9> to <12>, wherein the compound having a (meth) acryloyl group has an epoxy group.
<14> The curable resin composition according to any one of <9> to <13>, wherein the compound having a (meth) acryloyl group has an alicyclic epoxy group.
<15> The curable resin composition according to any one of <9> to <14>, further containing a curing accelerator.
<16> Any one of <9> to <15>, further comprising an inorganic filler, wherein the content of the inorganic filler is 70% by volume to 95% by volume with respect to the total volume of the curable resin composition 2. The curable resin composition according to item 1.
<17> The curable resin composition according to any one of <9> to <16>, further containing a coupling agent.
<18> An electronic component device comprising 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, it is possible to provide an electronic component device including an epoxy resin composition excellent in reflow resistance and an element sealed with the epoxy resin composition. *

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

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.

In the present disclosure, numerical ranges indicated using “to” indicate ranges including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, each component may contain a plurality of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of particles corresponding to each component may be included. When a plurality of particles corresponding to each component are present in the composition, the particle diameter of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, “(meth) acryloyl group” means at least one of acryloyl group and methacryloyl group, and “(meth) acryloyloxy group” means at least one of acryloyloxy group and methacryloyloxy group, “(Meth) acrylate” means at least one of acrylate and methacrylate, and “(meth) acrylic acid ester” means at least one of acrylic acid ester and methacrylic acid ester.

<Epoxy resin composition according to the first embodiment>
The epoxy resin composition according to the first embodiment includes (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, And (C) contains a curing agent. The epoxy resin composition may further contain other components as necessary. Hereinafter, (A) a monofunctional epoxy compound having one epoxy in one molecule is also simply referred to as “monofunctional epoxy compound”. In addition, (B) a polyfunctional epoxy compound having two or more epoxy groups in one molecule is also simply referred to as “polyfunctional epoxy compound”.

When the epoxy resin composition contains a monofunctional epoxy compound, an epoxy resin composition having excellent reflow resistance can be obtained. Although 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, an epoxy resin composition containing a monofunctional epoxy compound is not suitable as an epoxy resin. This is presumably because the crosslink density in the cured product is lower than the epoxy resin composition containing no functional epoxy compound, and the high temperature elastic modulus is lowered. In general, from the viewpoint of peeling stress during reflow, it is considered that the lower the high-temperature elastic modulus is, the more unlikely peeling occurs between the insert and the sealing material, and therefore excellent reflow resistance. Since the monofunctional epoxy compound has an epoxy group, it is excellent in reactivity, and as described above, the crosslink density is lowered to lower the elastic modulus, and the curability is considered to be sufficiently maintained.

(A) Monofunctional epoxy compound The epoxy resin composition contains a monofunctional epoxy compound. The monofunctional epoxy compound contained in the epoxy resin composition may be used alone or in combination of two or more.

The monofunctional epoxy compound is not particularly limited as long as it is a compound having one epoxy group in one molecule. The epoxy group contained in the monofunctional epoxy compound may be an alicyclic epoxy group such as an epoxycyclohexyl group or an acyclic epoxy group such as a glycidyl group. Monofunctional epoxy compound having one alicyclic epoxy group in one molecule (hereinafter also referred to as “monofunctional alicyclic epoxy compound”) and monofunctional epoxy having one acyclic epoxy group in one molecule A compound (hereinafter also referred to as “monofunctional acyclic epoxy compound”) may be used in combination. Hereinafter, each of (A1) monofunctional alicyclic epoxy compound and (A2) monofunctional acyclic epoxy compound will be described.

(A1) Monofunctional alicyclic epoxy compound The monofunctional alicyclic epoxy compound is not particularly limited as long as it is a monofunctional epoxy compound having one alicyclic epoxy group in one molecule. 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 is not particularly limited. The cycloaliphatic 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 even 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 containing an epoxy group, and n represents an integer of 0 to 10.
The monovalent substituent not containing the epoxy group represented by R is not particularly limited, and examples thereof include a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like, which may or may not have a substituent. Among these, an alkyl group is preferable, and a substituted alkyl group is preferable. When a plurality of R are present, the plurality of R may be the same or different.
n is preferably from 1 to 4, and 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 a group having a (meth) acryloyloxy group Is more preferable. When the monofunctional alicyclic epoxy compound has an ethylenically unsaturated double bond as a substituent of the alkyl group, the number of ethylenically unsaturated double bonds in the molecule in the monofunctional alicyclic epoxy compound is 1 May be two or more.

Examples of monofunctional alicyclic epoxy compounds include compounds represented by the following general formula (b).

In 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 to 9.
R ¹ is preferably a methyl group.
The definition and preferred embodiments of R ² are the same as the definition and preferred embodiments of R in formula (a).
n is preferably 0 to 3, and more preferably 0.
Among X, the divalent linking group is not particularly limited, and examples thereof include aliphatic hydrocarbons. Examples of the aliphatic hydrocarbon include a linear or branched alkylene group. When X is an alkylene group, the number of carbon atoms contained in the alkylene group is not particularly limited, preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. The alkylene group may have a substituent. In addition, the carbon number contained in the above-mentioned alkylene group shall not include the carbon number contained in a branch or a substituent.

Examples of the monofunctional alicyclic epoxy compound represented by the general formula (b) include a compound represented by the following formula (c).

Further examples of the monofunctional alicyclic epoxy compound include compounds represented by the following general formula (d).

In general formula (d), X represents a single bond or a divalent linking group. Among X, the divalent linking group is not particularly limited, and examples thereof include aliphatic hydrocarbons. Examples of the aliphatic hydrocarbon include a linear or branched alkylene group. When X is an alkylene group, the number of carbon atoms contained in the alkylene group is not particularly limited, and may be 1 to 10. The alkylene group may have a substituent. In addition, the carbon number contained in the above-mentioned alkylene group shall not include the carbon number contained in a branch or a substituent.

Examples of the monofunctional alicyclic epoxy compound represented by the general formula (d) include a compound represented by the following formula (e).

(A2) Monofunctional acyclic epoxy compound The monofunctional acyclic epoxy compound is not particularly limited as long as it is a monofunctional epoxy compound having one acyclic epoxy group in one molecule. Examples of the acyclic epoxy group include a glycidyl group and a glycidyloxy group.
The monofunctional acyclic epoxy compound is preferably a monofunctional epoxy compound having one acyclic epoxy group and a phenyl group in one molecule. As a compound having one acyclic epoxy group and a phenyl group in one molecule, a compound having one glycidyl group and a phenyl group in one molecule, and one glycidyloxy group in one molecule And compounds having a phenyl group. Especially, it is preferable that a monofunctional acyclic epoxy compound is a compound represented by the following general formula (f).

In the formula (f), R represents a monovalent substituent not containing an epoxy group, and n represents an integer of 0 to 5.
The monovalent substituent not containing the epoxy group represented by R is not particularly limited, and examples thereof include a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. 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 or may not have a substituent. When a plurality of R are present, the plurality of R may be the same or different. The substitution position of R is not particularly limited, and is preferably an ortho position or a para position.
n is preferably 0 to 3, and 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 the formula (g), R represents a monovalent substituent not containing an epoxy group, and n represents an integer of 0 to 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 to 2, and more preferably 0.

In the formula (h), R ¹ and R ² each independently represents a monovalent substituent not containing an epoxy group, p represents an integer of 0 to 4, and q represents an integer of 0 to 5.
The definition and preferred embodiment of the monovalent substituent not containing the 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 to 2, and more preferably 0. q is preferably from 0 to 3, more preferably 0.

As the monofunctional epoxy compound, a synthesized product or a commercially available product may be used. Examples of the monofunctional epoxy compound include 3,4-epoxycyclohexylmethyl methacrylate (for example, trade name: CYCLOMER M100, manufactured by Daicel Corporation), 4-t-butylphenyl glycidyl ether (for example, trade name: ED-509S). And 2-biphenylyl glycidyl ether (for example, trade name: EX-142, manufactured by Nagase ChemteX Corporation) and the like.

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

The epoxy equivalent of the monofunctional epoxy compound is not particularly limited. From the viewpoint of fluidity and reflow resistance, 500 g / eq or less is preferable, and 300 g / eq or less is more preferable.

The content of the monofunctional epoxy compound is preferably 1 part by mass to 30 parts by mass, more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound described later. The amount is more preferably from 25 parts by weight to 25 parts by weight, and particularly preferably from 10 parts by weight to 20 parts by weight. When the content of the monofunctional epoxy compound is 1 part by mass or more with respect to 100 parts by mass of the polyfunctional epoxy compound, the effect of reflow resistance tends to be sufficiently obtained. Moreover, when it is 30 parts by mass or less, a decrease in curability and releasability and generation of molding defects are suppressed, and handling properties tend to be improved.

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

(B) Polyfunctional epoxy compound The polyfunctional epoxy compound has two or more epoxy groups in one molecule. The polyfunctional epoxy compound may be one generally used in an epoxy resin composition, and the type thereof is not particularly limited as long as it has two or more epoxy groups in one molecule.

The polyfunctional epoxy compound may be an epoxy resin having two or more epoxy groups in one molecule. Specifically, at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolac type epoxy resin, which is obtained by epoxidizing a novolak resin obtained by condensing or co-condensing an organic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Orthocresol novolac type epoxy resin, etc.]; obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde in the presence of an acidic catalyst. Epoxidized triphenylmethane-type phenolic resin; epoxidized novolak resin obtained by co-condensation of the above phenolic and naphtholic compounds with an aldehyde compound under an acidic catalyst A diphenylidyl ether that is a diglycidyl ether such as bisphenol A or bisphenol F; a biphenyl type epoxy resin that is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a diglycidyl of a stilbene phenol compound Stilbene type epoxy resins that are ethers; sulfur atom-containing epoxy resins that are diglycidyl ethers such as bisphenol S; polymers such as butanediol, polyethylene glycol, and polypropylene glycol Epoxy resin that is glycidyl ether of chols; Glycidyl ester type epoxy resin that is glycidyl ester of polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, tetrahydrophthalic acid; Bonded to nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid Glycidylamine-type epoxy resin obtained by substituting the activated hydrogen with a glycidyl group; dicyclopentadiene-type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; epoxidizing intramolecular olefin bonds Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4) Epoxy) cycloaliphatic epoxy resin such as cyclohexane-m-dioxane; paraxylylene-modified epoxy resin that is glycidyl ether of paraxylylene-modified phenol resin; metaxylylene-modified epoxy resin that is glycidyl ether of metaxylylene-modified phenol resin; glycidyl ether of terpene-modified phenol resin Terpene-modified epoxy resin; dicyclopentadiene-modified epoxy resin, glycidyl ether of dicyclopentadiene-modified phenol resin; cyclopentadiene-modified epoxy resin, glycidyl ether of cyclopentadiene-modified phenol resin; glycidyl of polycyclic aromatic ring-modified phenol resin Polycyclic aromatic ring-modified epoxy resin which is ether; Naphthalene which is glycidyl ether of phenol resin containing naphthalene ring Ren type epoxy resin; Halogenated phenol novolak type epoxy resin; Hydroquinone type epoxy resin; Trimethylolpropane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid; Phenol aralkyl resin And an aralkyl type epoxy resin obtained by epoxidizing an aralkyl type phenol resin such as a naphthol aralkyl resin. Furthermore, an epoxidized product of a silicone resin, an epoxidized product of an acrylic resin, and the like are also exemplified as the epoxy resin. These epoxy resins may be used alone or in combination of two or more.

Among the above epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy from the viewpoint of balance between reflow resistance and fluidity An epoxy resin selected from the group consisting of a resin, a triphenylmethane type epoxy resin, a copolymer type epoxy resin and an aralkyl type epoxy resin (these are referred to as “specific epoxy resins”) is preferable. A specific epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type.

When the polyfunctional epoxy compound contains the specific epoxy resin, the content is preferably 30% by mass or more, and 50% by mass or more of the entire polyfunctional epoxy compound from the viewpoint of exhibiting the performance of the specific epoxy resin. It is more preferable.

Among specific epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins or sulfur atom-containing type epoxy resins are more preferable from the viewpoint of fluidity, and dicyclopentadiene type epoxy is preferable from the viewpoint of heat resistance. A resin, a triphenylmethane type epoxy resin or an aralkyl type epoxy resin is preferred. 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. Among the epoxy resins represented by the following general formula (II), the 3, 3 ′, 5, 5 ′ positions when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 ′ positions are methyl groups. There, YX-4000H (Mitsubishi Chemical Corporation, trade name) other ^{R 8} is a hydrogen atom, all the ^{R 8} are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, When all of R ⁸ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 ′ positions, the 3, 3 ′, 5, 5 ′ positions are methyl groups, and the other R YL-6121H (Mitsubishi Chemical Corporation, trade name), which is a mixture when ⁸ is a hydrogen atom, is commercially available.

In the formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, which may be all 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. Among the epoxy resins represented by the following general formula (III), 3, ⁹ ′, 5, 5 ′ positions are methyl groups when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′. And R ⁹ other than that is a hydrogen atom, and all of R ¹⁰ are hydrogen atoms, and three of the 3, ⁹ ′, 5, 5 ′ positions of R ⁹ are methyl groups, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixture of the case where one is a t-butyl group, the other R ⁹ is a hydrogen atom, and all of R ¹⁰ are hydrogen atoms, etc. It is available as a commercial product.

In the formula (III), R ⁹ and R ^{10 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all 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. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and 3, 3 when the positions where oxygen atoms are substituted in R ¹² are the 4 and 4 ′ positions. YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the ', 5,5'-position is a methyl group and the other R ¹² is a hydrogen atom is commercially available.

In the formula (IV), R ¹¹ and R ^{12 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each 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 with the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the 3 and 3 'positions when the positions where oxygen atoms are substituted in R ¹³ are the 4 and 4' positions are t-butyl groups, YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the 6,6′-position is a methyl group and the other R ¹³ is a hydrogen atom is commercially available.

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

The novolac type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolak resin, a cresol novolak resin, or a naphthol novolak resin using a method such as glycidyl etherification is preferable, and an epoxy represented by the following general formula (VI) A resin is more preferable. Among the epoxy resins represented by the following general formula (VI), all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, and i = 1, ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd.) , Trade names) etc. are available as commercial products.

In the formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, and each 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 Corporation, trade name) where i = 0 is available as a commercial product.

In the formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, which may be all 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 from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenol resin such as a novolak type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and is represented by the following general formula (VIII). An epoxy resin is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name), i is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name) Etc. are available as commercial products.

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

The copolymerization type epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton. . 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 an epoxy resin represented by the following general formula (IX) is more preferable. Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name) in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0 ) Etc. are available as commercial products.

In formula (IX), R ¹⁹ to R ²¹ each represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is independently an integer of 0 to 3, j is independently of an integer of 0 to 2, and k is independently of an integer of 0 to 4. Each of l and m is an average value and is a number from 0 to 10, and (l + m) is a number from 0 to 10. The terminal of the epoxy resin represented by the formula (IX) is one of the following formulas (IX-1) and (IX-2). In formulas (IX-1) and (IX-2), R ¹⁹ to R ²¹ are as defined for i, j and k, and R ¹⁹ to R ²¹ in formula (IX) are the same as the definitions for i, j and k. It is. n is 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).

Examples of the epoxy resin represented by the general formula (IX) include a random copolymer containing l constituent units and m constituent units at random, an alternating copolymer containing alternating units, and a copolymer containing regular units. And a block copolymer contained in a block form. Any one of these may be used alone, or two or more may be used in combination.

The aralkyl type epoxy resin is synthesized from 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 dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or derivatives thereof. If it is an epoxy resin which uses a phenol resin as a raw material, it will not be specifically limited. For example, a phenol resin synthesized from 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 dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or derivatives thereof An epoxy resin obtained by glycidyl etherification is preferable, and an epoxy resin represented by the following general formulas (X) and (XI) is more preferable.

Among the epoxy resins represented by the following general formula (X), i is 0, R- ³⁸ is a hydrogen atom, NC-3000S (Nippon Kayaku Co., Ltd., trade name), i is 0, R ³⁸ CER-3000 (Nippon Kayaku Co., Ltd., trade name), in which an epoxy resin in which hydrogen atom is a hydrogen atom and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms in a mass ratio of 80:20, is commercially available It is available as a product. Among 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 is commercially available. It is available as a product.

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

Regarding R ⁸ to R ²¹ and R ³⁷ to R ^{41 in the} above general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. The other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ also mean that all the numbers contained in the formula may be the same or different. R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different. For example, all of R ⁹ and R ¹⁰ may be the same or different.
In the general formulas (III) to (XI), the organic group having 1 to 18 carbon atoms is preferably an alkyl group or an aryl group.

In the above general formulas (II) to (XI), n is an average value and is preferably independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the epoxy resin composition decreases, poor filling, deformation of the bonding wire (gold wire connecting the element and the lead), etc. It tends to be suppressed. More preferably, n is set in the range of 0-4.

Specific examples of preferable polyfunctional epoxy compounds that can be used in the epoxy resin composition have been described above in accordance with the general formulas (II) to (XI). As more specific preferable polyfunctional epoxy compounds, reflow resistance From the viewpoint of the above, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is mentioned, and from the viewpoint of moldability and heat resistance, 4,4 ′ And '-bis (2,3-epoxypropoxy) -biphenyl.

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

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

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

(C) Curing agent
A hardening | curing agent may be what is generally used for the epoxy resin composition, and there is no restriction | limiting in particular.
Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. Among these, at least one selected from the group consisting of a phenol curing agent, an amine curing agent and an acid anhydride curing agent is preferable, and a phenol curing agent is more preferable.

Examples of the phenol curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. And at least one phenolic compound selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Novolac-type phenol resin obtained by condensation or co-condensation under a catalyst; the above phenolic compound, dimethoxyparaxylene, bis (methoxy Aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from methyl) biphenyl, etc .; paraxylylene and / or metaxylylene modified phenol resins; melamine modified phenol resins; terpene modified phenol resins; Dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization with pentadiene; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; the above-mentioned phenolic compound, benzaldehyde, Triphenylmethane type phenolic resin obtained by condensation or cocondensation with an aromatic aldehyde compound such as salicylaldehyde under an acidic catalyst; Phenol resins obtained by combined. These phenol curing agents may be used alone or in combination of two or more.

Among the phenol curing agents, from the viewpoint of reflow resistance, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, a copolymer type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and At least one selected from the group consisting of novolak-type phenolic resins (these are referred to as “specific phenol curing agents”) is preferable. A specific phenol hardening | curing agent may be used individually by 1 type, or may be used in combination of 2 or more type.

In the case where the curing agent contains a specific phenol curing agent, the content of the specific phenol curing agent is preferably 30% by mass or more, more preferably 50% by mass or more of the entire curing agent from the viewpoint of sufficiently exerting the performance. It is more preferable.

Examples of the aralkyl type phenol resin include a phenol aralkyl resin and a naphthol aralkyl resin synthesized from a phenolic compound, dimethoxyparaxylene, bis (methoxymethyl) biphenyl and the like. The aralkyl type phenol resin may be further copolymerized with another phenol resin. Examples of the copolymerized aralkyl type phenol resin include a copolymer type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, a copolymer type phenol resin of a salicylaldehyde type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. Examples thereof include copolymer type phenol resins with aralkyl type phenol resins.

The aralkyl type phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of a phenol compound and a naphthol compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or a derivative thereof. . For example, phenol resins represented by the following general formulas (XII) to (XIV) are preferable.

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

Among the phenol resins represented by the above general formula (XII), MEH-7851 (Maywa Kasei Co., Ltd., trade name) in which i is 0 and all R ²³ are hydrogen atoms is commercially available. .

Among the phenol resins represented by the general formula (XIII), XL-225, XLC (Mitsui Chemicals, trade name), MEH-7800 (Maywa Kasei Co., Ltd.), where i is 0 and k is 0 (Trade name) etc. are commercially available.

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

The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained using 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., trade name) in which i is 0 is available as a commercial product.

In the formula (XV), R ²⁹ represents a monovalent organic group having 1 to 18 carbon atoms, which may be all 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 using 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 (Maywa Kasei Co., Ltd., trade name) in which i is 0 and k is 0 is commercially available.

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

The copolymeric phenol resin of the benzaldehyde type phenol resin and the aralkyl type phenol resin is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin obtained using a compound having a benzaldehyde skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVII) is preferable.

Among phenol 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. It is available as a product.

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

The novolak-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of a phenol compound and a naphthol compound and an aldehyde compound under an acidic catalyst. . 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), Tamanols 758 and 759 (Arakawa Chemical Industries, Ltd., trade name) in which i is 0 and all R ³⁵ are hydrogen atoms, HP-850N (Hitachi Chemical) Co., Ltd., trade name) etc. are available as commercial products.

In the formula (XVIII), R ³⁵ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different. R ³⁶ represents a monovalent organic group having 1 to 18 carbon atoms, and each 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.

“All may be the same or different” described for R ²² to R ³⁶ in the general formulas (XII) to (XVIII) is, for example, that all i R ^{22s in} the formula (XII) are the same. But it means they can be different from each other. For the other R ²³ to R ³⁶ , it means that all of the numbers contained in the formula may be the same or different from each other. R ²² to R ³⁶ may be the same or different. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

In the above general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the epoxy resin composition also becomes low, unfilled defects, deformation of the bonding wire (gold wire connecting the element and the lead), etc. It becomes difficult to occur. The average n per molecule is preferably set in the range of 0-4.

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

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

The ratio of the total equivalent number of (A) monofunctional epoxy compound and (B) polyfunctional epoxy compound to the equivalent number of (C) curing agent, that is, the curing agent relative to the number of epoxy groups in the monofunctional epoxy compound and the multifunctional epoxy compound The ratio of the number of functional groups therein (the number of functional groups in the curing agent / the number of epoxy groups in the monofunctional epoxy compound and the polyfunctional epoxy compound) is not particularly limited. In order to reduce the amount of each unreacted component, it is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, the range of 0.8 to 1.2 is more preferable.

(D) Curing accelerator
The epoxy resin composition may contain a curing accelerator. As a hardening accelerator, what is generally used by the epoxy resin composition may be used, and there is no limitation in particular. Specifically, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 5,6-dibutylamino-1, Cycloamidine compounds such as 8-diazabicyclo [5.4.0] undec-7-ene; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2 , 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc. Compound having intramolecular polarization formed by adding a compound having π bond such as quinone compound, diazophenylmethane, phenol resin, etc .; Tertiary amine compounds such as tanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of these tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2 -Imidazole compounds such as heptadecylimidazole; derivatives of these imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; Phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, and phenol resin to a phosphine compound; Tetra-substituted phosphonium / tetra-substituted borates such as phenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate; 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / tetraphenyl Examples thereof include tetraphenylboron salts such as borates; derivatives of these tetrasubstituted phosphonium / tetrasubstituted borates and tetraphenylboron salts. These curing accelerators may be used alone or in combination of two or more.

Among them, the curing accelerator is preferably an adduct of a tertiary phosphine compound and a quinone compound from the viewpoint of curability and fluidity, and more preferably an adduct of triphenylphosphine and benzoquinone or an adduct of tributylphosphine and benzoquinone. preferable. From the viewpoint of storage stability, an adduct of a cycloamidine compound and a phenol resin is preferable, and a novolak-type phenol resin salt of diazabicycloundecene is more preferable. The content of the curing accelerator exemplified above is preferably 60% by mass or more, and more preferably 80% by mass or more, based on the total amount of the curing accelerator.

When an adduct of a third phosphine compound and a quinone compound is used as the curing accelerator, the total content of the adduct of the third phosphine compound and the quinone compound is preferably 60% by mass or more, based on the total amount of the curing accelerator, 80% by mass. % Or more is more preferable.

There is no restriction | limiting in particular as a tertiary phosphine used for the adduct of a tertiary phosphine and a quinone compound. Specifically, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine , Tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-butylphenyl) 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) phos Tertiary phosphine having an aryl group such as fin and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

Moreover, there is no restriction | limiting in particular as a quinone compound used for the adduct of a tertiary phosphine and a quinone compound. Specific examples include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone and the like. From the viewpoint of moisture resistance or storage stability, p-benzoquinone is preferred.

The content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, and (A) the monofunctional epoxy compound, (B) the polyfunctional epoxy compound, and (C) the curing agent. The amount is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass (hereinafter also referred to as “resin component”). There exists a tendency which time can be shortened as it is 0.1 mass part or more. Moreover, when it is 10 mass parts or less, it will be suppressed that a cure rate becomes quick too much, and there exists a tendency for a better molded article to be obtained.

(E) Inorganic filler
The epoxy resin composition may contain an inorganic filler. In particular, when the epoxy resin composition is used as a sealing material for 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, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite , Inorganic materials such as titania, talc, clay and mica. An inorganic filler having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as composite hydroxide of magnesium and zinc, zinc borate and the like. Among these, fused silica is preferable from the viewpoint of reducing 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, or may be used in combination of 2 or more type. Examples of the state of the inorganic filler include powder, beads formed by spheroidizing the powder, and fibers.

The average particle size of the inorganic filler is not particularly limited. Among these, from the viewpoint of moldability, the thickness 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 a laser diffraction scattering system particle size distribution measuring apparatus.

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

From the viewpoint of fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range.

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

The specific surface area of the inorganic filler is not particularly limited. Among these, from the viewpoint of moldability and strength, it is preferably 0.5 m ² / g to 12 m ² / g, and more preferably 1 m ² / g to 5 m ² / g. In addition, the specific surface area of an inorganic filler is measured from the nitrogen adsorption ability in 77K according to JISZ8830: 2013.

The content of the inorganic filler is not particularly limited, and is 70% by mass to 95% by mass in the epoxy resin composition from the viewpoint of improving flame retardancy, moldability, hygroscopicity and strength, and reducing the linear expansion coefficient. From the viewpoint of improving hygroscopicity and reducing the linear expansion coefficient, it is more preferably 85% by mass to 95% by mass. There exists a tendency for a flame retardance and reflow resistance to improve that the content rate of an inorganic filler is 70 mass% or more. Moreover, there exists a tendency which is excellent in fluidity | liquidity in it being 95 mass% or less. The content of the inorganic filler is preferably 70% to 95% by volume, more preferably 75% to 95% by volume, and more preferably 80% to 95% by volume with respect to the total volume of the epoxy resin composition. More preferably, it is 90 volume%. There exists a tendency for a flame retardance and reflow resistance to improve that the content rate of an inorganic filler is 70 volume% or more. Moreover, there exists a tendency which is excellent in fluidity | liquidity in it being 95 volume% or less.

[Various additives]
In addition to the above-mentioned components, the epoxy resin composition has various additions such as a coupling agent, an ion exchanger, an adhesion promoter, a release agent, a flame retardant, a colorant, a thermoplastic resin, and a stress relaxation agent exemplified below. An agent may be contained. The epoxy resin composition may contain various additives well known in the art as needed in addition to the additives exemplified below.

(Coupling agent)
When the epoxy resin composition contains an inorganic filler, a coupling agent may be contained in order to improve the adhesion between the resin component and the inorganic filler. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. . A coupling agent may be used individually by 1 type, or may be used in combination of 2 or more type.
Especially, it is preferable that a coupling agent contains a silane coupling agent. You may select the kind and number of organic functional groups other than the alkoxy silyl group and alkoxy silyl group in a silane coupling agent as needed.

When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler, and 0.1 parts by mass More preferably, it is ˜2.5 parts by mass. When the content of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesion with the frame tends to be further improved. When the content of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion exchanger)
The epoxy resin composition may contain an ion exchanger. In particular, when an epoxy resin composition is used as a molding material for sealing, an ion exchanger is included as necessary from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed. May be. An ion exchanger in particular is not restrict | limited, A conventionally well-known thing can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. An ion exchanger may be used individually by 1 type, or may be used in combination of 2 or more type. Especially, the hydrotalcite represented with 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, the content is not particularly limited as long as it is an amount sufficient to trap ions such as halogen ions. For example, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the resin component.

(Adhesion promoter)
The epoxy resin composition may contain an adhesion promoter as necessary from the viewpoint of further improving the adhesiveness. Specifically, derivatives such as imidazole, triazole, tetrazole, triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, derivatives thereof, aliphatic acid amide compounds, dithiocarbamates And thiadiazole derivatives. These adhesion promoters may be used alone or in combination of two or more.

(Release agent)
The epoxy resin composition may contain a release agent from the viewpoint of obtaining good release properties from the mold during molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. A mold release agent may be used individually by 1 type, or may be used in combination of 2 or more type.

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 with respect to 100 parts by mass of the resin component. When the content of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the release property tends to be sufficiently obtained. When the amount is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
An epoxy resin composition may contain a conventionally well-known flame retardant as needed from a viewpoint of the flame retardance improvement of a composition. Specifically, brominated epoxy resin; inorganic substance such as antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide; red phosphorus coated with thermosetting resin such as phenol resin; phosphate ester Phosphorus compounds such as melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; And the like, and the like.

_{_{_{p (M1 a O b) ·}}} q (M2 c O d) · m (H 2 O) ··· formula (II)

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

If M1 and M2 in the formula (II) are different metal elements, there is no particular limitation. From the viewpoint of flame retardancy, M1 is selected from the metal elements belonging to the third period metal element, group IIA alkaline earth metal element, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA. M2 is preferably selected from IIIB to IIB group transition metal elements, M1 is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M2 is iron, cobalt, nickel. More preferably, it is selected from copper and zinc. From the viewpoint of fluidity, it is preferable that M1 is magnesium and M2 is zinc or nickel. The ratio of p and q (p / q) is not particularly limited, and is preferably 1/99 to 1/1. The metal element is classified into a long-period periodic table in which the typical element is the A group and the transition element is the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987). (Reduced plate 30th printing).

Other flame retardants include compounds containing metal elements such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. 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. Among them, (A) 1 part by mass to 30 parts by mass is preferable with respect to 100 parts by mass of the epoxy resin, and 2 parts by mass to 15 parts by mass are more preferable.

(Coloring agent)
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 bengara. 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, or may be used in combination of 2 or more type.

(Thermoplastic resin)
The epoxy resin composition contains a thermoplastic resin such as an indene oligomer, which is a copolymer resin of styrenes such as polyphenylene ether, indene and alkylindene and styrenes such as styrene and alkylstyrene and phenols, as necessary. Good. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

(Stress relaxation agent)
The epoxy resin composition may contain a stress relaxation agent such as silicone oil and silicone rubber particles. By containing the stress relaxation agent, warpage deformation of the package and generation of package cracks can be further reduced. As a stress relaxation agent, the well-known stress relaxation agent (flexible agent) generally used is mentioned. Specifically, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, polybutadiene, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as MBS (methyl methacrylate-styrene-butadiene copolymer), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Examples thereof include rubber particles having a structure. A stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more type. Of these, silicone stress relieving agents are preferred. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

(Method for preparing epoxy resin composition)
The method for preparing the epoxy resin composition is not particularly limited. As a general technique, there can be mentioned a method in which various components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized. More specifically, for example, a method of stirring and mixing the various components described above, kneading with a kneader, roll, extruder, etc., which has been heated to 70 ° C. to 140 ° C. in advance, cooling, and crushing. it can.

The epoxy resin composition is preferably solid at room temperature and normal pressure (for example, 25 ° C. and atmospheric pressure). The shape in particular when an epoxy resin composition is solid is not restrict | limited, A powder form, a granular form, a tablet form etc. are mentioned. It is preferable from the viewpoint of handleability that the dimensions and mass when the epoxy resin composition is in the form of a tablet have dimensions and mass that match the molding conditions of the package.

<Electronic component apparatus according to the first embodiment>
The electronic component device according to the first embodiment includes an element sealed with the above-described epoxy resin composition.
Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates and other supporting members, active elements such as semiconductor chips, transistors, diodes, and thyristors, capacitors, and resistors. And an element portion obtained by mounting a passive element such as a coil) with an epoxy resin composition.
More specifically, the element is fixed on the lead frame, the terminal part of the element such as a bonding pad and the lead part are connected by wire bonding, bump, or the like, and then sealed by transfer molding or the like using an epoxy resin composition. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package T), SOJ (Small Outline J-Lead Package) ), General resin-sealed ICs such as TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure sealed with a resin composition; a structure in which an element connected to a wiring formed on a support member by wire bonding, flip chip bonding, solder or the like is sealed with an epoxy resin composition COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc., with the elements mounted on the surface of the support member with the wiring board connection terminals formed on the back, and formed on the elements and the support member by bump or wire bonding Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package), which have a structure in which an element is sealed with an epoxy resin composition after being connected to the formed wiring. Moreover, an epoxy resin composition can be used suitably also in a printed wiring board.

Examples of a method for sealing an electronic component device using an epoxy resin composition include a low-pressure transfer molding method, an injection molding method, and a compression molding method. Among these, the low-pressure transfer molding method is common.

<Curable resin composition according to the second embodiment>
The curable resin composition according to the second embodiment contains (A ′) a curable resin, (B ′) a curing agent, and (C ′) a compound having a (meth) acryloyl group. The curable resin composition may further contain other components as necessary. Hereinafter, a compound having a (C ′) (meth) acryloyl group may be referred to as a “specific acrylic compound”.

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

(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 is a compound having a (meth) acryloyl group.

The number of (meth) acryloyl groups contained in the specific acrylic compound is not limited, but is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1 or 2. In the present study, the specific acrylic compound preferably has a (meth) acryloyl group, and more preferably has a (meth) acryloyloxy group. In this study, the specific acrylic compound preferably contains a (meth) acrylic acid ester compound.

Specific examples of the specific acrylic compound include tricyclodecane dimethanol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. , Dicyclopentanyl (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.

The specific acrylic compound may be solid or liquid at normal temperature (25 ° C.), and is 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 to 320, more preferably 180 to 270, and still more preferably 190 to 220.

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

In a further embodiment, the specific acrylic compound may have an epoxy group. When the specific acrylic compound has an epoxy group, curability tends to be sufficiently maintained.
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.

Especially, it is preferable that a specific acrylic compound has an alicyclic epoxy group from viewpoints of reflow resistance, curability, etc. 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 carbon number of the cycloaliphatic skeleton of the alicyclic epoxy group is not particularly limited. The cycloaliphatic 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 even more preferably a 6-membered ring.

An example of the specific acrylic compound having an alicyclic epoxy group is a compound represented by the following general formula (a).

In 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 of 0 to 9.
R ¹ is preferably a methyl group.
The monovalent substituent represented by R ² is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. If R ² there are a plurality, the plurality of R ² may be the same or different.
Among X, the divalent linking group is not particularly limited, and examples thereof include aliphatic hydrocarbons. Examples of the aliphatic hydrocarbon include a linear or branched alkylene group. When X is an alkylene group, the number of carbon atoms contained in the alkylene group is not particularly limited, preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. The alkylene group may have an arbitrary substituent. In addition, the carbon number contained in the above-mentioned alkylene group shall not include the carbon number contained in a branch or a substituent.
n is preferably 0 to 3, and more preferably 0.

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

As the specific acrylic compound, a synthesized product or a commercially available product may be used. Examples of commercially available products include 3,4-epoxycyclohexylmethyl methacrylate (trade name: CYCLOMER M100, manufactured by Daicel Corporation).

The content of the specific acrylic compound is preferably 1 part by mass to 30 parts by mass, more preferably 5 parts by mass to 25 parts by mass, with respect to 100 parts by mass of the curable resin. More preferably, it is 10 parts by mass to 20 parts by mass. When the content of the specific acrylic compound is 1 part by mass or more with respect to 100 parts by mass of the curable resin, the fluidity is excellent and the effect of reflow resistance tends to be sufficiently obtained. Moreover, when it is 30 parts by mass or less, a decrease in curability and releasability and generation of molding defects are suppressed, and handling properties tend to be improved.

Further, the content of the specific acrylic compound is preferably 0.05 parts by mass to 2 parts by mass with respect to 100 parts by mass of the curable resin composition from the viewpoint of curability and releasability. More preferred is 1 part by mass to 1 part by mass.

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

(A ′) Curable 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 a reaction with a curing agent, a crosslinking agent, or the like.

The functional group causing the reaction of the curable resin is not particularly limited, and examples thereof include an acyclic epoxy group such as a glycidyl group, an alicyclic epoxy group, a hydroxyl group, a carboxy group, an amino group, an acryloyl group, and an isocyanate group. From the viewpoint of balance of properties as the sealing material, 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. The details of the epoxy resin when the curable resin is an epoxy resin are the same as the details of the (B) polyfunctional epoxy compound according to the first embodiment. In the description of the polyfunctional epoxy resin (B) according to the first embodiment, the description of “polyfunctional epoxy compound” is read as “epoxy resin”, and the description of “epoxy resin composition” is “curable resin”. "Composition".

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

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

(B ′) Curing Agent The curable resin composition contains a curing agent. The type of the curing agent is not particularly limited, and can be selected according to the type of the curable resin, the desired characteristics 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 according to the first embodiment. The details of the curing agent when the curable resin is an epoxy resin are the same as the details of the curing agent according to the first embodiment.
Note that the description of “epoxy resin composition” in the description of the curing agent according to the first embodiment is read as “curable resin composition”.
In the description of the curing agent according to the first embodiment, “the ratio between the total number of equivalents of (A) monofunctional epoxy compound and (B) polyfunctional epoxy compound and the number of equivalents of (C) curing agent, Description of “ratio of the number of functional groups in the curing agent to the number of epoxy groups in the functional epoxy compound and the polyfunctional epoxy compound (the number of functional groups in the curing agent / the number of epoxy groups in the monofunctional epoxy compound and the polyfunctional epoxy compound)” The equivalent ratio of the curable resin and the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (number of functional groups in the curing agent / number of functional groups in the curable resin) is read.

(D ′) Curing accelerator The curable resin composition may contain a curing accelerator. The details of the curing accelerator are the same as the details of the curing accelerator according to the first embodiment.
Note that the description of “epoxy resin composition” in the description of the curing accelerator according to the first embodiment is read as “curable resin composition”.
The “resin component” in the description of the content of the curing accelerator according to the first embodiment means “the total of the curable resin and the curing agent”.

(E ′) Inorganic filler The curable resin composition may contain an inorganic filler. The details of the inorganic filler are the same as the details of the inorganic filler according to the first embodiment.
The description of “epoxy resin composition” in the description of the inorganic filler according to the first embodiment is read as “curable resin composition”.

[Various additives]
In addition to the above-mentioned components, the curable resin composition includes various coupling agents, ion exchangers, adhesion promoters, mold release agents, flame retardants, colorants, thermoplastic resins, stress relaxation agents, and the like exemplified below. An additive may be contained. The details of the various additives are the same as the details of the various additives according to the first embodiment.
The description of “epoxy resin composition” in the description of various additives according to the first embodiment is read as “curable resin composition”.

(Method for preparing curable resin composition)
The method for preparing the curable resin composition is not particularly limited. The details of the method for preparing the curable resin composition are the same as the details of the method for preparing the epoxy resin composition according to the first embodiment. The description of “epoxy resin composition” in the description of the method for preparing an epoxy resin composition according to the first embodiment is read as “curable resin composition”.

<Electronic Component Device According to Second Embodiment>
The electronic component device according to the second embodiment includes an element sealed with the above-described curable resin composition. The details of the electronic component device are the same as the details of the electronic component device according to the first embodiment. Note that the description of “epoxy resin composition” in the description of the electronic component device according to the first embodiment is read as “curable resin composition”.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

[Example according to the first embodiment]
(Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-5)
The following components were blended in the amounts shown in Table 1 and Table 2 below (unit: parts by mass) and roll kneaded under conditions of a kneading temperature of 100 ° C. and a kneading time of 10 minutes. Examples 1-1 to 1-8 And the epoxy resin compositions of Comparative Examples 1-1 to 1-5 were prepared. Note that the blank in the table represents “no formulation”.

The following were used as monofunctional epoxy compounds of the examples.
Epoxy compound 1: Epoxy compound represented by formula (c) having an epoxy equivalent of 196 g / eq (manufactured by Daicel Corporation, CYCLOMER M100)
Epoxy compound 2: 2-biphenylyl glycidyl ether having an epoxy equivalent of 226 g / eq

The following were used as comparative epoxy compounds.
Epoxy compound 3: a bifunctional alicyclic epoxy compound having an epoxy equivalent of 126 g / eq (CELLOXIDE 2021 manufactured by Daicel Corporation)

The following was used as the polyfunctional epoxy compound (polyfunctional epoxy compound having two or more epoxy groups in one molecule).
Polyfunctional epoxy compound 4: Epoxy equivalent 250 g / eq, methoxynaphthalene type epoxy resin having a softening point of 58 ° C. (manufactured by DIC Corporation, HP-5000)
Polyfunctional epoxy compound 5: phenol aralkyl type epoxy resin containing biphenylene skeleton having an epoxy equivalent of 241 g / eq and a softening point of 96 ° C. (manufactured by Nippon Kayaku Co., Ltd., CER-3000L)
Polyfunctional epoxy compound 6: biphenylene aralkyl type epoxy resin having an epoxy equivalent of 282 g / eq and a softening point of 56 ° C. (manufactured by Nippon Kayaku Co., Ltd., NC-3000)

As the curing agent, a xylylene type phenol resin (MEHC-7800SS, manufactured by Meiwa Kasei Co., Ltd.) having a hydroxyl group equivalent of 175 g / eq and a softening point of 70 ° C. was used.
As the curing 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.
As other additive components, carnauba wax and carbon black were used.

[Evaluation of epoxy resin composition]
The properties of the epoxy resin compositions prepared in Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-5 were evaluated by the following property tests (1) to (5). The evaluation results are shown in Tables 1 and 2 below. The epoxy resin composition was molded 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 unless otherwise specified. Further, post-curing was performed at 175 ° C. for 5 hours as necessary.

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

(2) Hardness during heating The epoxy resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness tester (manufactured by Ueshima Seisakusho, HD-1120 (Type D)) was used. And measured.

(3) 260 ° C shear adhesive strength
Under the above conditions, the epoxy resin composition was formed on a silver-plated copper plate into a size having a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm, and post-cured under the above conditions. Thereafter, using a series 4000 manufactured by Nordson Advanced Technology Co., Ltd., the shear adhesive strength (MPa) was determined at a shear rate of 50 μm / s while keeping the temperature of the copper plate at 260 ° C.

(4) Water absorption rate
The disk molded in the above (2) was post-cured under the above conditions. Then, the obtained disc was left for 168 hours under the conditions of 85 ° C. and 60% RH, and the mass change before and after being left was measured. The water absorption was calculated from the measurement result according to the following formula.
Water absorption (mass%) = {(disc mass after standing−disc mass before leaving) / disc mass before leaving} × 100

(5) Reflow resistance
An 80-pin flat package (QFP) (lead frame material: copper alloy, die pad upper surface and lead-plated silver plated product) with an external dimension of 20 mm x 14 mm x 2 mm mounted with a silicon chip of 8 mm x 10 mm x 0.4 mm The resin composition was molded under the above conditions and post-cured under the above conditions. The obtained package was humidified for 168 hours at 85 ° C. and 85% RH. Thereafter, a reflow process is performed at 250 ° C., 260 ° C., or 270 ° C. for 10 seconds, and the presence or absence of cracks inside the package is visually observed. It was observed with a construction machine manufactured by HYE-FOCUS. The reflow resistance was evaluated by the total number of packages in which either cracks or peeling occurred with respect to the number of test packages (10).

As shown in Table 1 and Table 2, Examples 1-1 to 1-8 containing a monofunctional epoxy compound were compared with Comparative Examples 1-1 to 1-5 not containing a monofunctional epoxy compound. Excellent reflow resistance at 260 ° C. or higher. Further, the curability was sufficiently maintained.
Further, among Examples 1-1 to 1-5, Examples 1-1, 1-3, 1 in which the content of the monofunctional epoxy compound is 5 parts by mass to 20 parts by mass with respect to the polyfunctional epoxy compound. -4 and 1-5 were excellent in spiral flow and tended to show good fluidity.

[Example according to the second embodiment]
(Examples 2-1 to 2-7, Comparative Examples 2-1 to 2-5)
The following components were blended in the amounts shown in Table 3 and Table 4 below (unit: parts by mass) and roll kneaded under conditions of a kneading temperature of 100 ° C. and a kneading time of 10 minutes. Examples 2-1 to 2-7 Also, curable resin compositions of Comparative Examples 2-1 to 2-5 were prepared. Note that the blank in the table represents “no formulation”.

The following were used as the specific acrylic compounds in the examples.
Specific acrylic compound 1: epoxy compound represented by formula (b) having an epoxy equivalent of 196 g / eq (CYCLOMER M100, manufactured by Daicel Corporation)

The following compounds were used as comparative compounds.
-Comparative compound 1: bifunctional alicyclic epoxy compound having an epoxy equivalent of 126 g / eq (Daicel Co., Ltd., CELLOXIDE 2021; (meth) acryloyl group-free)

The following was used as the curable resin.
Epoxy resin 1: methoxynaphthalene type epoxy resin having an epoxy equivalent of 250 g / eq and a softening point of 58 ° C. (manufactured by DIC Corporation, HP-5000)
Epoxy resin 2: epoxy equivalent 241 g / eq, phenol aralkyl type epoxy resin containing biphenylene skeleton having a softening point of 96 ° C. (CER-3000L, manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 3: biphenylene aralkyl type epoxy resin having an epoxy equivalent of 282 g / eq and a softening point of 56 ° C. (manufactured by Nippon Kayaku Co., Ltd., NC-3000)

[Evaluation of curable resin composition]
The characteristics of the curable resin compositions prepared in Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-5 were evaluated by the following characteristic tests (1) to (5). The evaluation results are shown in Tables 3 and 4 below. The curable resin composition was molded 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 unless otherwise specified. Further, post-curing was performed at 175 ° C. for 5 hours as necessary.

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

(2) Hardness under heat A curable resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness meter (manufactured by Ueshima Seisakusho, HD-1120 (Type D)) It measured using.

(3) 260 ° C shear adhesive strength
Under the above conditions, the curable resin composition was molded into a silver-plated copper plate with a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm, and post-cured under the above conditions. Thereafter, using a series 4000 manufactured by Nordson Advanced Technology Co., Ltd., the shear adhesive strength (MPa) was determined at a shear rate of 50 μm / s while keeping the temperature of the copper plate at 260 ° C.

(5) Reflow resistance
Curing 80mm flat package (QFP) (lead frame material: copper alloy, die pad top surface and lead tip silver-plated product) with external dimensions of 20mm x 14mm x 2mm mounted with 8mm x 10mm x 0.4mm silicon chip The resin composition was molded under the above conditions and post-cured under the above conditions. The obtained package was humidified for 168 hours at 85 ° C. and 85% RH. Thereafter, a reflow process is performed at 250 ° C., 260 ° C., or 270 ° C. for 10 seconds, and the presence or absence of cracks inside the package is visually observed. It was observed with a construction machine manufactured by HYE-FOCUS. The reflow resistance was evaluated by the total number of packages in which either cracks or peeling occurred with respect to the number of test packages (10).

As shown in Tables 3 and 4, Examples 2-1 to 2-7 containing the specific acrylic compound were compared with Comparative Examples 2-1 to 2-5 not containing the specific acrylic compound, in particular 260 ° C. The reflow resistance in the above was excellent. Further, the hardness at the time of heating was sufficiently maintained.
In addition, among Examples 2-1 to 2-5, Examples 2-1 to 2-2 have a specific acrylic compound content of 5 to 20 parts by mass with respect to the polyfunctional epoxy compound. Nos. 4 and 2-5 were excellent in spiral flow and tended to show good fluidity.

The disclosures of Japanese Patent Application No. 2017-072118 filed on March 31, 2017 and Japanese Patent Application No. 2017-0721119 filed on March 31, 2017 are hereby incorporated by reference in their entirety. Is taken in. All documents, patent applications, and technical standards described in this specification are to the same extent as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

A monofunctional epoxy compound having one epoxy group in one molecule;
An epoxy resin composition comprising a polyfunctional epoxy compound having two or more epoxy groups in one molecule, and a curing agent.
The epoxy resin composition according to claim 1, wherein the monofunctional epoxy compound includes a monofunctional epoxy compound having one alicyclic epoxy group in one molecule.
The epoxy resin composition according to claim 1, wherein the monofunctional epoxy compound includes a monofunctional epoxy compound having one acyclic epoxy group and a phenyl group in one molecule.
The epoxy resin composition according to any one of claims 1 to 3, wherein a content of the monofunctional epoxy compound with respect to 100 parts by mass of the polyfunctional epoxy compound is 1 part by mass to 30 parts by mass.
The epoxy resin composition according to any one of claims 1 to 4, further comprising a curing accelerator.
6. The inorganic filler according to claim 1, further comprising an inorganic filler, wherein the content of the inorganic filler is 70% by volume to 95% by volume with respect to the total volume of the epoxy resin composition. The epoxy resin composition as described.
The epoxy resin composition according to any one of claims 1 to 6, further comprising a silane coupling agent.
An electronic component device comprising an element sealed with the epoxy resin composition according to any one of claims 1 to 7.
A curable resin composition containing a curable resin, a curing agent, and a compound having a (meth) acryloyl group.
The curable resin composition according to claim 9, wherein the compound having a (meth) acryloyl group has a molecular weight of 180 to 320.
The curable resin composition according to claim 9 or 10, wherein the compound having a (meth) acryloyl group contains a (meth) acrylic acid ester compound.
The curable resin composition according to any one of claims 9 to 11, wherein the compound having a (meth) acryloyl group has an alicyclic structure.
The curable resin composition according to any one of claims 9 to 12, wherein the compound having a (meth) acryloyl group has an epoxy group.
The curable resin composition according to any one of claims 9 to 13, wherein the compound having a (meth) acryloyl group has an alicyclic epoxy group.
The curable resin composition according to any one of claims 9 to 14, further comprising a curing accelerator.
The inorganic filler is further contained, and the content of the inorganic filler is 70% by volume to 95% by volume with respect to the total volume of the curable resin composition. The curable resin composition described in 1.
The curable resin composition according to any one of claims 9 to 16, further comprising a coupling agent.
An electronic component device comprising an element sealed with the curable resin composition according to any one of claims 9 to 17.