JPWO2018181384A1 - Epoxy resin composition, curable resin composition, and electronic component device - Google Patents

Abstract

The epoxy resin composition contains 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. The curable resin composition contains a curable resin, a curing agent, and a compound having a (meth) acryloyl group. Further, the electronic component device includes an element sealed with an epoxy resin composition or a curable resin composition.

Description

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

  2. Description of the Related Art In recent years, as electronic devices have become smaller, lighter, and have higher performance, mounting density has been increasing. As a result, the mainstream of electronic component devices is changing from a conventional pin insertion type package to a surface mount type package such as an IC (Integrated Circuit) and an LSI (Large Scale Integration).

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

  In order to meet the above requirements, various studies have been made on the epoxy resin as a main material from the viewpoint of reducing moisture absorption. Further, from the viewpoint of improving the adhesion to an insert such as an element lead frame, use of a silane coupling agent as a modifier for an inorganic filler contained in a sealing material is being studied. 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), and the like. Are being considered.

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

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

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

  A second embodiment of the present disclosure has an object 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 is 1 part by mass to 30 parts by mass based on 100 parts by mass of the polyfunctional epoxy compound.
<5> The epoxy resin composition according to any one of <1> to <4>, further comprising a curing accelerator.
<6> Any one of <1> to <5>, further containing an inorganic filler, wherein the content of the inorganic filler is 70% by volume to 95% by volume based on the total volume of the epoxy resin composition. Item 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 including an element sealed with the epoxy resin composition according to any one of <1> to <7>.

Further, means for solving the above 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 contains a (meth) acrylate 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 of <9> to <15>, further containing an inorganic filler, wherein the content of the inorganic filler is 70% by volume to 95% by volume based on the total volume of the curable resin composition. 9. The curable resin composition according to claim 1.
<17> The curable resin composition according to any one of <9> to <16>, further containing a coupling agent.
<18> An electronic component device including an element sealed with the curable resin composition according to any one of <9> to <17>.

  According to the first embodiment of the present disclosure, it is possible to provide an epoxy resin composition having excellent reflow resistance, and an electronic component device including 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 having excellent 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 the element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and does not limit the present invention.

In the present disclosure, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively.
In the numerical ranges described in stages in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. . Further, in the numerical range described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
In the present disclosure, each component may include a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content or content of each component is, unless otherwise specified, the total content or content of the plurality of substances present in the composition. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value of a mixture of the plurality of types of particles present in the composition unless otherwise specified.
In the present disclosure, “(meth) acryloyl group” means at least one of an acryloyl group and a methacryloyl group, and “(meth) acryloyloxy group” means at least one of an acryloyloxy group and a methacryloyloxy group, “(Meth) acrylate” means at least one of acrylate and methacrylate, and “(meth) acrylate” means at least one of acrylate and methacrylate.

<Epoxy resin composition according to 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) a curing agent. The epoxy resin composition may further contain other components as necessary. Hereinafter, (A) the monofunctional epoxy compound having one epoxy in one molecule is also simply referred to as “monofunctional epoxy compound”. Further, (B) the 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 having excellent 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 a simple epoxy resin. This is presumed to be because the crosslink density in the cured product is lower than that of the epoxy resin composition containing no functional epoxy compound, and the high-temperature elastic modulus is lower. Generally, from the viewpoint of the peeling stress at the time of reflow, it is considered that the lower the high-temperature elastic modulus is, the more difficult it is for the peeling to occur between the insert and the sealing material, and thus the more excellent the reflow resistance is. The monofunctional epoxy compound has excellent reactivity because of having an epoxy group, and it is considered that the curability is sufficiently maintained while the elastic modulus is lowered by lowering the crosslink density as described above.

(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 compound 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) the monofunctional alicyclic epoxy compound and (A2) the 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 a cyclic aliphatic skeleton.
The number of carbon atoms in the cyclic aliphatic skeleton is not particularly limited. The cyclic aliphatic skeleton is, for example, preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 6-membered ring.
The alicyclic structure may or may not contain an unsaturated bond, and may or may not have a substituent.

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

In the general formula (a), R represents a monovalent substituent not containing an epoxy group, and n represents an integer of 0 to 10.
The monovalent substituent not containing an 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, and these may or may not have a substituent. Among these, an alkyl group is preferred, and a substituted alkyl group is preferred. When a plurality of Rs are present, the plurality of Rs may be the same or different.
n is preferably from 1 to 4, more preferably 1.

  When R is a substituted alkyl group, the substituent of the alkyl group is preferably a group having an ethylenically unsaturated double bond, more preferably a group having a (meth) acryloyl group, and a group having a (meth) acryloyloxy group. Is more preferred. 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 of the monofunctional alicyclic epoxy compound is 1; May be two or more.

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

In the general formula (b), R ¹ represents a hydrogen atom or a methyl group. R ² represents a monovalent substituent containing no epoxy group. X represents a single bond or a divalent linking group. n represents the integer of 0-9.
R ¹ is preferably a methyl group.
The definition and preferred embodiment of R ² are the same as the definition and preferred embodiment of R in formula (a).
n is preferably 0 to 3, and more preferably 0.
Among X, the divalent linking group is not particularly limited, and examples thereof include an aliphatic hydrocarbon. 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 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. The alkylene group may have a substituent. Note that the number of carbon atoms contained in the above-described alkylene group does not include the number of carbon atoms 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).

  A further example of the monofunctional alicyclic epoxy compound is a compound represented by the following general formula (d).

  In the 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 an aliphatic hydrocarbon. 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. Note that the number of carbon atoms contained in the above-described alkylene group does not include the number of carbon atoms 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. Examples of the compound having one acyclic epoxy group and a phenyl group in one molecule include a compound having one glycidyl group and one phenyl group in one molecule and one glycidyloxy group in one molecule. And a compound having a phenyl group. Among them, the monofunctional acyclic epoxy compound is preferably 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 an 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, branched, or 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 Rs are present, the plurality of Rs 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 formulas (g) and (h).

In the formula (g), R represents a monovalent substituent containing no epoxy group, and n represents an integer of 0 to 4.
The definition and preferred embodiment of R in the compound represented by the formula (g) are the same as the definition and preferred embodiment of R in the compound represented by the formula (f).
n is preferably from 0 to 2, and more preferably 0.

In the formula (h), R ¹ and R ² each independently represent 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 an 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 from 0 to 2, and more preferably 0. q is preferably 0 to 3, and more preferably 0.

  As the monofunctional epoxy compound, a synthesized one may be used, or a commercially available product may be used. As the monofunctional epoxy compound, for example, 3,4-epoxycyclohexylmethyl methacrylate (for example, trade name: CYCLOMER M100, manufactured by Daicel Corporation), 4-t-butylphenylglycidyl ether (for example, trade name: ED-509S) ADEKA), 2-biphenylylglycidyl 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 room 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, the content is preferably 500 g / eq or less, more preferably 300 g / eq or less.

  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, and more preferably 5 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound described below. Parts by mass to 25 parts by mass, more preferably 10 parts by mass to 20 parts by mass. 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. When the amount is 30 parts by mass or less, curability and releasability are reduced, and occurrence of molding failure is suppressed, and handling properties tend to be improved.

  Further, 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 mold release properties, Parts to 1 part by mass is more preferred.

(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 its type 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, bisphenol F and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak epoxy resin obtained by condensing or co-condensing an acidic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde and propionaldehyde under an acidic catalyst (phenol novolak epoxy resin, Orthocresol novolak type epoxy resin); obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane-type epoxy resin obtained by epoxidizing a triphenylmethane-type phenol resin obtained by epoxidizing a novolak resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound under an acidic catalyst. A diphenylmethane-type epoxy resin which is a diglycidyl ether of bisphenol A or bisphenol F; a biphenyl-type epoxy resin which is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a diglycidyl stilbene phenol compound Stilbene type epoxy resins which are ethers; sulfur atom-containing epoxy resins which are diglycidyl ethers such as bisphenol S; a such as butanediol, polyethylene glycol and polypropylene glycol. Epoxy resin which is a glycidyl ether of coals; Glycidyl ester type epoxy resin which is a glycidyl ester of polycarboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; Bonds to nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid Glycidylamine-type epoxy resin obtained by replacing activated hydrogen with a glycidyl group; dicyclopentadiene-type epoxy resin obtained by epoxidizing a cocondensation resin of dicyclopentadiene and a phenol compound; epoxidation of olefin bond in the molecule Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4 Epoxy) alicyclic epoxy resin such as cyclohexane-m-dioxane; paraxylylene-modified epoxy resin which is a glycidyl ether of para-xylylene-modified phenol resin; meta-xylylene-modified epoxy resin which is a glycidyl ether of meta-xylylene-modified phenol resin; glycidyl ether of a terpene-modified phenol resin A terpene-modified epoxy resin; a dicyclopentadiene-modified phenolic resin glycidyl ether; a dicyclopentadiene-modified epoxy resin; a cyclopentadiene-modified phenolic resin glycidyl ether; a cyclopentadiene-modified epoxy resin; a polycyclic aromatic ring-modified phenolic resin Polycyclic aromatic ring-modified epoxy resin which is ether; naphtha which is glycidyl ether of naphthalene ring-containing phenol resin Len type epoxy resin; halogenated phenol novolak type epoxy resin; hydroquinone type epoxy resin; trimethylol propane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; phenol aralkyl resin Aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as naphthol aralkyl resins. Further, epoxidized products of silicone resin, epoxidized products of acrylic resin, and the like are also included as epoxy resins. These epoxy resins may be used alone or in combination of two or more.

  Among the above epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin An epoxy resin selected from the group consisting of a resin, a triphenylmethane type epoxy resin, a copolymerization type epoxy resin and an aralkyl type epoxy resin (these are referred to as “specific epoxy resins”) is preferred. The specific epoxy resin may be used alone or in combination of two or more.

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

  Among the specific epoxy resins, from the viewpoint of fluidity, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin or sulfur atom-containing type epoxy resin is more preferable, from the viewpoint of heat resistance, dicyclopentadiene type epoxy resin Resins, triphenylmethane type epoxy resins or aralkyl type epoxy resins are preferred. Hereinafter, specific examples of preferred epoxy resins are shown.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable. In the epoxy resin represented by the following general formula (II), when R ⁸ is substituted with an oxygen atom at the 4 and 4 ′ positions, the 3,3 ′, 5,5 ′ position is a methyl group. YX-4000H in which R ⁸ is a hydrogen atom (Mitsubishi Chemical Corporation, trade name), 4,4′-bis (2,3-epoxypropoxy) biphenyl in which all R ⁸ are hydrogen atoms, When all R ⁸ are hydrogen atoms, and when R ⁸ is substituted with an oxygen atom at 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 mixed product when ⁸ is a hydrogen atom, and the like are 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, all of which may be the same or different. n is an average value and shows the number of 0-10.

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), when R ⁹ is substituted with an oxygen atom at positions 4 and 4 ′, the 3,3 ′, 5,5 ′ positions are methyl groups. R ⁹ is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3,3 ′, 5,5 ′ positions of R ⁹ are methyl groups, One is a t-butyl group, the other R ⁹ is a hydrogen atom, and all of R ¹⁰ are hydrogen atoms. It is available as a commercial product.

In the formula (III), R ⁹ and R ¹⁰ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. n is an average value and shows the number of 0-10.

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 when R ¹² is substituted with an oxygen atom at positions 4 and 4 ′, 3,3 YSLV-80XY (trade name of Nippon Steel & Sumikin Chemical Co., Ltd.) in which the ', 5,5'-positions are 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, all of which may be the same or different. n is an average value and shows the number of 0-10.

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) is given. Among the epoxy resins represented by the following general formula (V), when the position at which the oxygen atom is substituted in R ¹³ is the 4 and 4 ′ position, the 3,3 ′ position is a t-butyl group, YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd.) 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, all of which may be the same or different. n is an average value and shows the number of 0-10.

The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolak resin, a cresol novolak resin, and a naphthol novolak resin using a method such as glycidyl etherification is preferable, and an epoxy resin represented by the following formula (VI) Resins are more preferred. 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 and ESCN-195 (Sumitomo Chemical Co., Ltd.) , Trade names) are commercially available.

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

  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 the 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, all of which may be the same or different. i represents an integer of 0 to 3 each independently. n is an average value and shows the number of 0-10.

  The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin such as a novolak-type phenol resin 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). Epoxy resin is more preferred. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and iPN is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name) Are available as commercial products.

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

The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound and a phenol compound and an aldehyde compound is not particularly limited as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. . For example, an epoxy resin obtained by glycidyl etherification of a novolak 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 in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0 (Nippon Kayaku Co., Ltd., trade name) ) And the like are commercially available.

In the formula (IX), R ^{19 to} R ²¹ represent a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, and k is each independently an integer of 0 to 4. l and m are each an average value and a number from 0 to 10, and (l + m) indicates 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 formula (IX-1) and ^{(IX-2), R 19} ~R 21 is, i, ^R 19 ^{to R 21} the definitions of j and k in the formula (IX), i, as defined in 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 randomly, an alternating copolymer containing alternately, and a copolymer containing regularly. , Block copolymers and the like. 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. The phenol resin is not particularly limited as long as it is an epoxy resin using phenol resin as a raw material. 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 Is preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

Among the epoxy resins represented by the following general formula (X), NC-3000S (Nippon Kayaku Co., Ltd., trade name) in which i is 0 and R ³⁸ is a hydrogen atom, i is 0, and R ³⁸ CER-3000 (Nippon Kayaku Co., Ltd., trade name) in which an epoxy resin having a hydrogen atom and an epoxy resin of the general formula (II) in which all R ⁸ is a hydrogen atom are mixed at a mass ratio of 80:20 is commercially available. Available as a product. Among the epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name) in which i is 0, j is 0, and k is 0 is commercially available. 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, all of which 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 all may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, and l is each independently an integer of 0 to 6. Show. n is an average value and is a number of 0 to 10 each independently.

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, ^{8 to} R 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 of the respective numbers included in the formula may be the same or different. Further, 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.
Further, the organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

  N in the above general formulas (II) to (XI) 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 during melt molding of the epoxy resin composition decreases, poor filling, deformation of a bonding wire (a gold wire connecting the element and the lead), and the like. Tends to be suppressed. n is more preferably set in the range of 0 to 4.

As described above, specific examples of preferable polyfunctional epoxy compounds usable in the epoxy resin composition have been described along the general formulas (II) to (XI). From the viewpoint of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl, from the viewpoint of moldability and heat resistance, '-Bis (2,3-epoxypropoxy) -biphenyl.

  In addition to the above, from the viewpoint of low warpage, a dihydroanthracene-type epoxy resin which is a diglycidyl ether of an alkyl-substituted or aromatic-substituted or unsubstituted anthracene (for example, Mitsubishi Chemical Corporation product name: YX-8800) 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, HP-5000, trade name of DIC Corporation).

  The epoxy equivalent of the polyfunctional epoxy compound is not particularly limited. From the viewpoint of the 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 150 g / eq to 500 g / eq. More preferably, there is.

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

(C) Curing agent
The curing agent may be one generally used in an epoxy resin composition, and is not particularly limited.
Examples of the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent. Among them, 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 a phenol resin having two or more phenolic hydroxyl groups in one molecule and a polyhydric phenol compound. Specifically, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. Phenolic compounds 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. A novolak-type phenol resin obtained by condensation or co-condensation in the presence of a catalyst; the above phenolic compound, dimethoxyparaxylene, bis (methoxy) Phenol aralkyl resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from methyl) biphenyl and the like; para-xylylene and / or meta-xylylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; Dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization with pentadiene; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; Triphenylmethane-type phenolic resin obtained by condensation or co-condensation 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 phenol resin, a dicyclopentadiene phenol resin, a triphenylmethane phenol resin, a copolymer phenol resin of a benzaldehyde phenol resin and an aralkyl phenol resin, and At least one selected from the group consisting of novolak-type phenol resins (these are referred to as “specific phenol curing agents”) is preferred. The specific phenol curing agent may be used alone or in combination of two or more.

  When the curing agent contains a specific phenolic curing agent, the content of the specific phenolic curing agent is preferably 30% by mass or more, and more preferably 50% by mass or more, from the viewpoint of sufficiently exhibiting their performance. Is more preferable.

  Examples of the aralkyl-type phenolic resin include a phenolic aralkyl resin and a naphthol aralkyl resin synthesized from a phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or the like. The aralkyl-type phenol resin may be further copolymerized with another phenol resin. Copolymerized aralkyl-type phenolic resins include benzaldehyde-type phenolic resins and aralkyl-type phenolic resins, salicylaldehyde-type phenolic resins and aralkyl-type phenolic resins, and novolak-type phenolic resins. A phenol resin copolymerized with an aralkyl phenol resin is exemplified.

  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 preferred.

In the formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which 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 all may be 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, all of which may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, p is each independently an integer of 0 to 4 is there. n is an average value and is a number of 0 to 10 each independently.

Among the phenolic resin of formula (XII), i is 0, MEH-7851 R ²³ are all hydrogen atoms (Meiwa Kasei Co., trade name) and the like are commercially available .

  Among the phenolic resins represented by the general formula (XIII), XL-225, XLC (trade name, Mitsui Chemicals, Inc.), MEH-7800 (Meiwa Kasei Co., Ltd., wherein i is 0 and k is 0) Are commercially available.

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

  The dicyclopentadiene-type phenol resin is not particularly limited as long as it is obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among the phenolic resins represented by the following general formula (XV), DPP (i.e., 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, all of which may be the same or different. i represents an integer of 0 to 3 each independently. n is an average value and shows the number of 0-10.

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

  Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (Meiwa 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 all may be 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 copolymerized phenolic resin of benzaldehyde-type phenolic resin and aralkyl-type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of phenolic resin and aralkyl-type phenolic 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 the phenolic resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., trade name) in which i is 0, k is 0, and q is 0 is commercially available. 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 all may be the same or different. i is each independently an integer of 0 to 3, k is each independently an integer of 0 to 4, and q is each independently an integer of 0 to 5. l and m are each an average value, and are each independently a number from 0 to 11. Here, the sum of l and m is a number of 1 to 11.

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

Among the phenol resins represented by the following general formula (XVIII), i is ^{0, R 35} are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (Hitachi Chemical (Trade name) is available as a commercial product.

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

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) means that, for example, all of i R ^{22 in} the formula (XII) are the same. However, it means that they may be different from each other. The other R ^{23 to} R ³⁶ also mean that all of the respective numbers included in the formula may be the same or different from each other. Further, 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.

  N in the above general formulas (XII) to (XVIII) preferably ranges from 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the epoxy resin composition at the time of melt molding becomes low, and poor filling and deformation of a bonding wire (a gold wire connecting the element and the lead) are caused. Less likely to occur. The average n in one molecule is preferably set in the range of 0 to 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 the balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably from 70 g / eq to 1000 g / eq, and more preferably from 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 from 40 ° C to 180 ° C, and from the viewpoint of handleability during production of the epoxy resin composition, it is more preferably from 50 ° C to 130 ° C.

  The ratio of the total equivalent number of (A) the monofunctional epoxy compound and (B) the polyfunctional epoxy compound to the equivalent number of the (C) curing agent, that is, the curing agent to the number of epoxy groups in the monofunctional epoxy compound and the polyfunctional epoxy compound. The ratio of the number of functional groups in the composition (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. From the viewpoint of reducing the amount of each unreacted component, the content is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoints of moldability and reflow resistance, it is more preferable to set the range to 0.8 to 1.2.

(D) Curing accelerator
The epoxy resin composition may contain a curing accelerator. The curing accelerator may be one generally used in an epoxy resin composition, and is not particularly limited. 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; and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, , 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc. Compounds having an intramolecular polarization obtained by adding a compound having a π bond such as a quinone compound, diazophenylmethane, or a phenol resin; Tertiary amine compounds such as tert-amine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; derivatives of these tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, Imidazole compounds such as heptadecyl imidazole; derivatives of these imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine; Phosphorus compound having intramolecular polarization obtained 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 borate such as phenylphosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate; 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / tetraphenyl Tetraphenylboron salts such as borate; and derivatives of these tetrasubstituted phosphonium / tetrasubstituted borates and tetraphenylboron salts. One of these curing accelerators may be used alone, or two or more thereof may be used in combination.

  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 phenol resin salt of diazabicycloundecene is more preferable. The content of the curing accelerator exemplified above is preferably 60% by mass or more, more preferably 80% by mass or more, based on the total amount of the curing accelerator.

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

  The tertiary phosphine used in the adduct of the tertiary phosphine and the quinone compound is not particularly limited. 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) phosphine Tertiary phosphine having an aryl group such as fin and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.

  The quinone compound used for the adduct of the tertiary phosphine and the quinone compound is not particularly limited. Specific examples include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. 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 the content of (A) the monofunctional epoxy compound, (B) the polyfunctional epoxy compound, and (C) the curing agent The amount is preferably from 0.1 to 10 parts by mass, more preferably from 0.3 to 5 parts by mass, per 100 parts by mass of the total (hereinafter also referred to as “resin component”). When the amount is 0.1 parts by mass or more, the time tends to be shortened. On the other hand, when the amount is 10 parts by mass or less, the curing speed is prevented from becoming too fast, and a better molded product tends 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 the 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 , Titania, talc, clay, mica and the like. 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, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Among them, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One inorganic filler may be used alone, or two or more inorganic fillers may be used in combination. Examples of the state of the inorganic filler include powder, beads obtained by making the powder spherical, fibers, and the like.

  The average particle size of the inorganic filler is not particularly limited. Above all, from the viewpoint of moldability, the thickness is preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm. The average particle size of the inorganic filler is measured as a volume average particle size using a laser diffraction / scattering type particle size distribution analyzer.

  The volume average particle size 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, or the like, and sufficiently dispersed using an ultrasonic disperser or the like 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 type particle size distribution analyzer. Alternatively, the volume average particle diameter of the inorganic filler is measured from the volume-based particle size distribution obtained by embedding the cured product in a transparent epoxy resin or the like and observing a cross section obtained by polishing with a scanning electron microscope. Can be. Further, the measurement can also be performed by continuously observing a two-dimensional cross section of the cured product using a FIB apparatus (focused ion beam SEM) or the like and performing a three-dimensional structure analysis.

  From the viewpoint of the 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 wide.

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

The specific surface area of the inorganic filler is not particularly limited. Among them from the viewpoints of moldability and ^strength, it is preferably 0.5m ² / g~12m 2 / ^g, and more preferably 1m ² / g~5m 2 / g. The specific surface area of the inorganic filler is measured from the nitrogen adsorption capacity at 77K according to JIS Z 8830: 2013.

  The content of the inorganic filler is not particularly limited, and is preferably 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 coefficient of linear expansion. It is more preferably from 85% by mass to 95% by mass from the viewpoint of improving the hygroscopicity and reducing the linear expansion coefficient. When the content of the inorganic filler is 70% by mass or more, flame retardancy and reflow resistance tend to be improved. When the content is 95% by mass or less, the fluidity tends to be excellent. Further, the content of the inorganic filler is preferably from 70% by volume to 95% by volume, more preferably from 75% by volume to 95% by volume, and more preferably from 80% by volume, based on the total volume of the epoxy resin composition. More preferably, it is 90% by volume. When the content of the inorganic filler is 70% by volume or more, flame retardancy and reflow resistance tend to be improved. When the content is 95% by volume or less, the fluidity tends to be excellent.

[Various additives]
The epoxy resin composition includes, in addition to the components described above, various additives 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 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 enhance the adhesiveness 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. . One type of coupling agent may be used alone, or two or more types may be used in combination.
Among them, the coupling agent preferably contains a silane coupling agent. The type and number of the alkoxysilyl group and the organic functional group other than the alkoxysilyl group in the silane coupling agent may be selected as necessary.

  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 part 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 based on 100 parts by mass of the inorganic filler, the adhesiveness to the frame tends to be further improved. When the content of the coupling agent is 5 parts by mass or less based on 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 the epoxy resin composition is used as a molding material for sealing, an ion exchanger is optionally contained from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including the element to be sealed. May be. The ion exchanger is not particularly limited, and a conventionally known ion exchanger can be used. Specific examples include a hydrotalcite compound and a hydrated oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. One type of ion exchanger may be used alone, or two or more types may be used in combination. Among them, hydrotalcite represented by the following general formula (A) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (A)
(0 <X ≦ 0.5, m is a positive number)

  When the epoxy resin composition contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 5 parts by mass, per 100 parts by mass of the resin component.

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

(Release agent)
The epoxy resin composition may contain a release agent from the viewpoint of obtaining good mold releasability from the mold during molding. The release agent is not particularly limited, and a conventionally known release agent 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 polyethylene oxide and non-oxidized polyethylene. One type of release agent may be used alone, or two or more types may be used in combination.

  When the epoxy resin composition contains a release agent, the content is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the resin component. When the content of the release agent is 0.01 parts by mass or more based on 100 parts by mass of the resin component, there is a tendency that sufficient releasability is obtained. When the amount is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The epoxy resin composition may contain a conventionally known flame retardant, if necessary, from the viewpoint of improving the flame retardancy of the composition. Specifically, brominated epoxy resins; inorganic substances such as antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, and zinc oxide; red phosphorus coated with a thermosetting resin such as a phenol resin; phosphate ester A nitrogen-containing compound such as a melamine, a melamine derivative, a melamine-modified phenolic resin, a compound having a triazine ring, a cyanuric acid derivative, an isocyanuric acid derivative; a phosphorus and a nitrogen-containing compound such as cyclophosphazene; And a composite metal hydroxide represented by the formula:

_{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.

  M1 and M2 in the formula (II) are not particularly limited as long as they are different metal elements. From the viewpoint of flame retardancy, M1 is selected from a metal element belonging to the third period, a group IIA alkaline earth metal, a group IVB, a group IIB, a group VIII, a group IB, a group IIIA and a group IVA. , M2 are preferably selected from the group IIIB-IIB transition metal elements, M1 is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M2 is iron, cobalt, nickel , Copper and zinc are more preferred. Further, 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 classification of the metal elements is based on a long-period periodic table in which the typical elements are in the A sub-group and the transition elements are in the B sub-group (Source: Chemical Dictionary 4 by Kyoritsu Shuppan Co., Ltd., February 15, 1987) This is performed on the basis of a reduced printing 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, dicyclopentadienyl iron, and the like. 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, the amount is preferably from 1 to 30 parts by mass, more preferably from 2 to 15 parts by mass, per 100 parts by mass of the epoxy resin (A).

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

(Thermoplastic resin)
The epoxy resin composition contains a thermoplastic resin such as an indene oligomer which is a copolymer resin of an indene such as polyphenylene ether, indene and alkyl indene and a styrene and a phenol such as styrene and alkyl styrene as needed. Good. The thermoplastic resins may be used alone or in combination of two or more.

(Stress relaxation agent)
The epoxy resin composition may contain a stress relieving agent such as silicone oil and silicone rubber particles. By containing the stress relaxation agent, warpage of the package and occurrence of package cracks can be further reduced. Examples of the stress relaxing agent include well-known stress relaxing agents (flexible agents) that are generally used. Specifically, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic Rubber particles such as rubber, urethane rubber and silicone powder, core-shell such as MBS (methyl methacrylate-styrene-butadiene copolymer), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer And rubber particles having a structure. One type of stress relaxation agent may be used alone, or two or more types may be used in combination. Among them, silicone-based stress relaxation agents are preferred. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, and those modified with polyether.

(Method of preparing epoxy resin composition)
The method for preparing the epoxy resin composition is not particularly limited. As a general method, 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 can be exemplified. More specifically, for example, a method of stirring and mixing the above-described various components, kneading with a kneader, a roll, an extruder or the like that has been heated to 70 to 140 ° C. in advance, cooling, and pulverizing may be mentioned. it can.

  The epoxy resin composition is preferably solid at normal temperature and normal pressure (for example, 25 ° C. and atmospheric pressure). The shape when the epoxy resin composition is solid is not particularly limited, and examples thereof include powder, granule, and tablet. When the epoxy resin composition is in the form of a tablet, it is preferable from the viewpoint of handleability that the dimensions and the mass be such as to meet the molding conditions of the package.

<Electronic component device according to 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 supporting members such as lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, as well as active elements such as semiconductor chips, transistors, diodes, and thyristors, capacitors, and resistors. , A passive element such as a coil, etc.) and sealing the element part with an epoxy resin composition.
More specifically, the device is fixed on a lead frame, and the terminal portion of the device such as a bonding pad and the lead portion are connected by wire bonding, bumps, 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, SOJ (Small Outline Package), SOJ (Small Outline Package, SOJ) ), TQFP (Thin Quad Flat Package) and other general resin-sealed ICs; 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. A chip on board (COB) module, a hybrid IC, a multi-chip module, etc .; an element is mounted on a surface of a support member having terminals for connection to a wiring board formed on the back surface, and formed on the element and the support member by bump or wire bonding. After connection with the wiring thus formed, BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which the element is sealed with an epoxy resin composition are exemplified. Also, the epoxy resin composition can be suitably used for a printed wiring board.

  Examples of a method for sealing an electronic component device using the 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 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, the compound having a (C ′) (meth) acryloyl group may be referred to as a “specific acrylic compound”.

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

(C ′) Specific acrylic compound The curable resin composition contains a specific acrylic compound. The specific acrylic compound may be used singly or in combination of two or more. The specific acrylic compound is not particularly limited as long as it has 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 even more preferably 1 or 2. In this 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) acrylate 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 room 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 from 180 to 320, more preferably from 180 to 270, even more preferably from 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, the 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.

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

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

In the general formula (a), R ¹ represents a hydrogen atom or a methyl group. R ² represents a monovalent substituent. X represents a single bond or a divalent linking group. n represents the integer of 0-9.
R ¹ is preferably a methyl group.
The monovalent substituent represented by R ² is not particularly limited, and includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like. 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 an aliphatic hydrocarbon. 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 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. The alkylene group may have any substituent. Note that the number of carbon atoms contained in the above-described alkylene group does not include the number of carbon atoms 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 (3,4-epoxycyclohexylmethyl methacrylate) represented by the following formula (b).

  As the specific acrylic compound, a synthesized one or a commercially available product may be used. 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, and more preferably 5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the curable resin. Is more preferably 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. When the amount is 30 parts by mass or less, curability and releasability are reduced, and occurrence of molding failure is 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 viewpoints of curability and releasability, and 0.1 mass Parts to 1 part by mass is more preferred.

  Whether or not the specific acrylic compound is included in the curable resin composition can be confirmed, for example, by measuring the mass spectrum 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 one that is cured by self-polymerization or one that is cured by a reaction with a curing agent, a crosslinking agent, or the like.

  The functional group that causes 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 the balance of properties as a sealing material, a curable resin containing a cyclic ether group is preferable, and a curable resin containing an epoxy group (epoxy resin) 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. Details of the epoxy resin when the curable resin is an epoxy resin are the same as the details of (B) the polyfunctional epoxy compound according to the first embodiment. In the description of the polyfunctional epoxy resin (B) according to the first embodiment, the description “polyfunctional epoxy compound” is replaced with “epoxy resin”, and the description “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 150 g / eq to 500 g / eq. More preferably, there is.

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

(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, desired characteristics of the curable resin composition, and the like.
When the curable resin is an epoxy resin, examples of the curing agent 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.
In addition, the description of the "epoxy resin composition" in the description of the curing agent according to the first embodiment is replaced with the term "curable resin composition".
In the description of the curing agent according to the first embodiment, “the ratio of the total number of equivalents of (A) the monofunctional epoxy compound and (B) the polyfunctional epoxy compound to the equivalent number of the curing agent (C), that is, The description of “the 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)” is “curing”. Equivalent ratio between 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 (the number of functional groups in the curing agent / the number of functional groups in the curable resin).

(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.
In addition, the description of the “epoxy resin composition” in the description of the curing accelerator according to the first embodiment is replaced with the “curable resin composition”.
Further, 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.
In addition, the description of the “epoxy resin composition” in the description of the inorganic filler according to the first embodiment is replaced with the “curable resin composition”.

[Various additives]
The curable resin composition includes, in addition to the components described above, various types of coupling agents, ion exchangers, adhesion promoters, release agents, flame retardants, coloring agents, thermoplastic resins, stress relaxation agents, and the like exemplified below. It may contain additives. Details of the various additives are the same as the details of the various additives according to the first embodiment.
In addition, the description of the “epoxy resin composition” in the description of the various additives according to the first embodiment is replaced with the “curable resin composition”.

(Preparation method of curable resin composition)
The method for preparing the curable resin composition is not particularly limited. The details of the method of preparing the curable resin composition are the same as the details of the method of preparing the epoxy resin composition according to the first embodiment. In the description of the method for preparing the epoxy resin composition according to the first embodiment, the term “epoxy resin composition” is replaced with “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. In the description of the electronic component device according to the first embodiment, “epoxy resin composition” is replaced with “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, “parts” 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 (unit: parts by mass) shown in Tables 1 and 2, respectively, and kneaded in a roll at a kneading temperature of 100 ° C. and a kneading time of 10 minutes. And, the epoxy resin compositions of Comparative Examples 1-1 to 1-5 were respectively prepared. The blanks in the table indicate "no compounding".

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

The following epoxy compounds were used for comparison.
Epoxy compound 3: 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 (a polyfunctional epoxy compound having two or more epoxy groups in one molecule).
-Polyfunctional epoxy compound 4: methoxynaphthalene type epoxy resin having an epoxy equivalent of 250 g / eq and a softening point of 58 ° C (HP-5000, manufactured by DIC Corporation)
Polyfunctional epoxy compound 5: Biphenylene skeleton-containing phenol aralkyl type epoxy resin having an epoxy equivalent of 241 g / eq and a softening point of 96 ° C. (CER-3000L, manufactured by Nippon Kayaku Co., Ltd.)
Polyfunctional epoxy compound 6: Biphenylene aralkyl type epoxy resin having an epoxy equivalent of 282 g / eq and a softening point of 56 ° C (Nippon Kayaku Co., Ltd., NC-3000)

As a curing agent, a xylylene-type phenol resin (MEHC-7800SS, manufactured by Meiwa Kasei Co., Ltd.) having a hydroxyl equivalent of 175 g / eq and a softening point of 70 ° C was used.
A betaine-type adduct of triphenylphosphine and p-benzoquinone was used as a curing accelerator.
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.
Carnauba wax and carbon black were used as other additional components.

[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 molding of the epoxy resin composition was performed by a transfer molding machine at a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds unless otherwise specified. Post-curing was performed at 175 ° C. for 5 hours as needed.

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

(2) Hot Hardness 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. Immediately after molding, a Shore D type hardness meter (HD-1120 (type D) manufactured by Kamishima Seisakusho Co., Ltd.) was used. It measured using.

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

(4) Water absorption
The disk formed in the above (2) was post-cured under the above conditions. Thereafter, the obtained disc was left under conditions of 85 ° C. and 60% RH for 168 hours, and the change in mass before and after the standing was measured. From the measurement results, the water absorption was calculated by the following equation.
Water absorption (mass%) = {(disc mass after standing-disc mass before standing) / disc mass before standing} x 100

(5) Reflow resistance
An 80-pin flat package (QFP) with an external dimension of 20 mm x 14 mm x 2 mm (8 mm x 10 mm x 0.4 mm silicon chip mounted) (lead frame material: copper alloy, die pad top surface and silver plating at the tip of the lead) is epoxy The resin composition was molded under the above conditions and post-cured under the above conditions. The obtained package was humidified under the conditions of 85 ° C. and 85% RH for 168 hours. Thereafter, reflow treatment is performed at a temperature of 250 ° C., 260 ° C., or 270 ° C. for 10 seconds, and the presence or absence of cracks inside the package is visually checked by using an ultrasonic flaw detector (Hitachi, Ltd.). (HYE-FOCUS manufactured by Construction Machinery Co., Ltd.). The reflow resistance was evaluated based on the total number of packages in which any of cracks and peeling occurred with respect to the number of test packages (10).

As shown in Tables 1 and 2, Examples 1-1 to 1-8 containing the monofunctional epoxy compound were compared with Comparative Examples 1-1 to 1-5 not containing the monofunctional epoxy compound, The reflow resistance at 260 ° C. or higher was excellent. Also, the curability was sufficiently maintained.
Further, among Examples 1-1 to 1-5, Examples 1-1, 1-3 and 1 wherein the content of the monofunctional epoxy compound is 5 to 20 parts by mass with respect to the polyfunctional epoxy compound. -4 and 1-5 tended to exhibit excellent spiral flow and 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 (unit: parts by mass) shown in Tables 3 and 4 below, and roll kneading was performed under the conditions of a kneading temperature of 100 ° C. and a kneading time of 10 minutes. And the curable resin composition of Comparative Examples 2-1 to 2-5 was prepared, respectively. The blanks in the table indicate "no compounding".

The following were used as 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 for comparison.
Comparative Compound 1: Bifunctional alicyclic epoxy compound having an epoxy equivalent of 126 g / eq (manufactured by Daicel Corporation, CELLOXIDE 2021; containing no (meth) acroyl group)

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

As a curing agent, a xylylene-type phenol resin (MEHC-7800SS, manufactured by Meiwa Kasei Co., Ltd.) having a hydroxyl equivalent of 175 g / eq and a softening point of 70 ° C was used.
A betaine-type adduct of triphenylphosphine and p-benzoquinone was used as a curing accelerator.
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.
Carnauba wax and carbon black were used as other additional components.

[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 molding of the curable resin composition was performed by a transfer molding machine at a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds unless otherwise specified. Post-curing was performed at 175 ° C. for 5 hours as needed.

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

(2) Hot Hardness The curable 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 type hardness meter (HD-1120 (type D), manufactured by Kamishima Seisakusho Co., Ltd.) It measured using.

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

(4) Water absorption
The disk formed in the above (2) was post-cured under the above conditions. Thereafter, the obtained disc was left under conditions of 85 ° C. and 60% RH for 168 hours, and the change in mass before and after the standing was measured. From the measurement results, the water absorption was calculated by the following equation.
Water absorption (mass%) = {(disc mass after standing-disc mass before standing) / disc mass before standing} x 100

(5) Reflow resistance
Hardened 80-pin flat package (QFP) with external dimensions of 20 mm x 14 mm x 2 mm (8 mm x 10 mm x 0.4 mm silicon chip mounted) (lead frame material: copper alloy, die pad top surface and silver plating at the tip of the lead) The resin composition was molded under the above conditions and post-cured under the above conditions. The obtained package was humidified under the conditions of 85 ° C. and 85% RH for 168 hours. Thereafter, reflow treatment is performed at a temperature of 250 ° C., 260 ° C., or 270 ° C. for 10 seconds, and the presence or absence of cracks inside the package is visually checked by using an ultrasonic flaw detector (Hitachi, Ltd.). (HYE-FOCUS manufactured by Construction Machinery Co., Ltd.). The reflow resistance was evaluated based on the total number of packages in which any of cracks and 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, and particularly at 260 ° C. The reflow resistance described above was excellent. Further, the hardness when heated was sufficiently maintained.
Further, among Examples 2-1 to 2-5, Examples 2-1 to 2-3, in which the content of the specific acrylic compound is 5 to 20 parts by mass with respect to the polyfunctional epoxy compound. In Nos. 4 and 2-5, the spiral flow was excellent and there was a tendency to show good fluidity.

  The disclosures of Japanese Patent Application No. 2017-072118 filed on Mar. 31, 2017 and Japanese Patent Application No. 2017-072119 filed on Mar. 31, 2017 are incorporated herein by reference in their entireties. It is taken in. All documents, patent applications, and technical standards referred to in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (18)

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 the content of the monofunctional epoxy compound is 1 part by mass to 30 parts by mass based on 100 parts by mass of the polyfunctional epoxy compound.   The epoxy resin composition according to any one of claims 1 to 4, further comprising a curing accelerator.   The inorganic filler according to any one of claims 1 to 5, wherein the content of the inorganic filler is 70% by volume to 95% by volume based on the total volume of the epoxy resin composition. The epoxy resin composition according to the above.   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 claim 1.   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, wherein the compound having a (meth) acryloyl group includes a (meth) acrylate 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, The content rate of the said inorganic filler is 70 volume%-95 volume% with respect to the total volume of the said curable resin composition, any one of Claims 9-15. 3. The curable resin composition according to item 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.