JP2020063404A - Epoxy resin composition and electronic component device - Google Patents

Abstract

To provide an epoxy resin composition having excellent reflow resistance, and an electronic component device having an element sealed with the epoxy resin composition.SOLUTION: The present invention provides an epoxy resin composition containing an epoxy resin, a phenol curing agent, and a cyclic amide compound, and an electronic component device having an element sealed with the epoxy resin composition.SELECTED DRAWING: None

Description

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

  2. Description of the Related Art As electronic devices have become smaller, lighter, and have higher performance in recent years, mounting density has been increasing. As a result, the mainstream of electronic component devices is changing from conventional pin-insertion type packages to surface mount type packages such as ICs (Integrated Circuits) and LSIs (Large Scale Integrations).

  The surface mount type package is different in mounting method from the conventional pin insertion type package. That is, when the pins are attached to the wiring board, the conventional pin insertion type package does not directly expose the package to high temperature because the pins are inserted into the wiring board and then soldering is performed from the back surface of the wiring board. However, in the surface mount type package, the entire electronic component device is processed by the solder bath, the reflow device, and the like, so that the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture due to moisture absorption expands rapidly during soldering, and the generated vapor pressure acts as peeling stress, causing peeling between the insert such as the element and lead frame and the sealing material. If they are generated, they may cause package cracks, defective electrical characteristics, and the like. Therefore, it is desired to develop a sealing material that has excellent adhesiveness to the insert and, by extension, excellent solder heat resistance (reflow resistance).

  In order to meet the above requirements, the use of a silane coupling agent as a modifier for the inorganic filler contained in the encapsulant has been investigated. Specifically, use of an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent (for example, refer to Patent Document 1), use of a sulfur atom-containing silane coupling agent (for example, refer to Patent Document 2), etc. Is being considered.

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

  However, at present, an epoxy resin composition that sufficiently satisfies the reflow resistance has not been obtained. In view of the above circumstances, it is an object of the present disclosure to provide an epoxy resin composition having excellent reflow resistance, and an electronic component device including an element sealed with the epoxy resin composition.

Means for solving the above problems include the following embodiments.
<1> An epoxy resin composition containing an epoxy resin, a phenol curing agent, and a cyclic amide compound.
<2> The epoxy resin composition according to <1>, wherein the cyclic amide compound contains at least one selected from the group consisting of ε-caprolactam and derivatives thereof.
<3> The epoxy resin composition according to <1> or <2>, in which the content of the cyclic amide compound is 0.01% by mass to 10.0% by mass.
<4> The epoxy resin composition according to any one of <1> to <3>, which further contains a curing accelerator.
<5> The epoxy resin composition according to any one of <1> to <4>, which further contains an inorganic filler.
<6> An electronic component device including an element sealed with the epoxy resin composition according to any one of <1> to <5>.

  According to the present disclosure, it is possible to provide an electronic component device including an epoxy resin composition having excellent reflow resistance and an element sealed with the epoxy resin composition.

  Hereinafter, modes 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 constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.

In the present disclosure, the numerical range indicated by using "to" indicates the range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. . Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, the content rate or content of each component in the composition refers to the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means the total content rate or content.
In the present disclosure, the particle size of each component in the composition is a plurality of types of particles corresponding to each component in the composition, unless otherwise specified, with respect to a mixture of the plurality of types of particles present in the composition. Means the value of.

<Epoxy resin composition>
The epoxy resin composition of the present disclosure contains an epoxy resin, a phenol curing agent, and a cyclic amide compound. The epoxy resin composition may further contain other components, if necessary.

  The studies conducted by the present inventors have revealed that the epoxy resin composition containing a cyclic amide compound makes it possible to obtain an epoxy resin composition having excellent reflow resistance. Although the detailed reason for this is not always clear, when a cyclic amide compound is used in the epoxy resin composition, the crosslink density of the cured product decreases due to ring-opening polymerization of the cyclic amide compound as compared with the case where no cyclic amide compound is used. It is presumed that this is because the high temperature elastic modulus decreases. In general, from the viewpoint of peeling stress during reflow, it is considered that the lower the high temperature elastic modulus is, the more difficult the peeling occurs between the insert and the sealing material, and the better the reflow resistance is.

(Cyclic amide compound)
The epoxy resin composition of the present disclosure contains a cyclic amide compound. The cyclic amide compound contained in the epoxy resin composition may be used alone or in combination of two or more kinds. The cyclic amide compound is not particularly limited as long as it is a compound having a cyclic amide structure.

  The cyclic amide compound is preferably a compound represented by the following general formula (1).

  In general formula (1), R represents a hydrogen atom or an organic group, and X represents a hydrocarbon chain which is bonded to an amide group to form a ring structure.

In general formula (1), R represents a hydrogen atom or an organic group, and is preferably a hydrogen atom. When R represents an organic group, examples of the organic group include a saturated or unsaturated hydrocarbon group. Examples of the saturated or unsaturated hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted vinyl group and the like.
In the general formula (1), X represents a hydrocarbon chain that is bonded to an amide group to form a ring structure. The number of atoms contained in the ring structure is not particularly limited, but the cyclic amide compound is preferably a 3-membered ring to a 10-membered ring, more preferably a 5-membered ring to a 9-membered ring, and a 7-membered ring. Is more preferable. The hydrocarbon chain represented by X may or may not have a substituent. Examples of the substituent include organic groups such as alkyl groups and hydroxyl groups. The carbon atom contained in the hydrocarbon chain represented by X or its substituent may be bonded to the nitrogen atom or R to form a ring structure.

  Examples of the cyclic amide compound include α-lactam, β-lactam, γ-lactam, δ-lactam, ε-lactam (ε-caprolactam), and derivatives thereof. From the viewpoint of easy availability, at least one selected from the group consisting of ε-caprolactam and its derivatives is preferable. In addition, in the present disclosure, the derivative of the cyclic amide compound refers to a compound in which a hydrogen atom in a hydrocarbon chain forming a ring is substituted with a substituent. Examples of the substituent include organic groups such as alkyl groups and hydroxyl groups.

  The content of the cyclic amide compound in the epoxy resin composition is not particularly limited, but from the viewpoint of reflow resistance, the total of the epoxy resin contained in the epoxy resin composition and the curing agent used as necessary (hereinafter, "resin"). It is also preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, and further preferably 3.0 parts by mass or more with respect to 100 parts by mass. From the viewpoint of curability, for example, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less, relative to 100 parts by mass of the resin component.

(Epoxy resin)
The epoxy resin composition of the present disclosure contains an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
Specifically, at least one phenol selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, phenol compounds such as bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Type compound, formaldehyde, acetaldehyde, a novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation of an aliphatic aldehyde compound such as propionaldehyde under an acidic catalyst (phenol novolak type epoxy resin, Orthocresol novolac type epoxy resin, etc.); obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenolic resin; epoxidized novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst A copolymer type epoxy resin; a diphenylmethane type epoxy resin which is a diglycidyl ether of bisphenol A, bisphenol F, etc .; 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 resin which is ether; sulfur atom-containing epoxy resin which is diglycidyl ether such as bisphenol S; butanediol, polyethylene glycol, polypropylene glycol and the like Epoxy resin which is glycidyl ether of coal; glycidyl ester type epoxy resin which is glycidyl ester of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; bonded to nitrogen atom such as aniline, diaminodiphenylmethane and isocyanuric acid Glycidylamine type epoxy resin obtained by substituting active hydrogen with glycidyl group; Dicyclopentadiene type epoxy resin obtained by epoxidizing co-condensation resin of dicyclopentadiene and phenol compound; Epoxidation of olefin bond in molecule Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4 Epoxy) cycloaliphatic-epoxy resin such as cyclohexane-m-dioxane; paraxylylene-modified epoxy resin that is a glycidyl ether of paraxylylene-modified phenol resin; metaxylylene-modified epoxy resin that is a glycidyl ether of metaxylylene-modified phenol resin; glycidyl ether of 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 glycidyl Polycyclic aromatic ring-modified epoxy resin which is an ether; naphtha which is a glycidyl ether of a naphthalene ring-containing phenol resin Len type epoxy resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; phenol aralkyl resin , An aralkyl-type epoxy resin obtained by epoxidizing an aralkyl-type phenol resin such as a naphthol aralkyl resin. Further, epoxy resin such as epoxy resin of silicone resin and epoxy resin of acrylic resin can also be used. These epoxy resins may be used alone or in combination of two or more.

  Among the above epoxy resins, from the viewpoint of balance between reflow resistance and fluidity, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy. 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 resin”) is preferable. The specific epoxy resins may be used alone or in combination of two or more.

  When the epoxy resin contains a specific epoxy resin, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more, from the viewpoint of exhibiting the performance of the specific epoxy resin. .

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

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable. Among the epoxy resins represented by the following general formula (II), 3,8 ', 5' and 5'positions are methyl groups when the positions where oxygen atoms are substituted in R ⁸ are 4 and 4'positions. There, YX-4000H (Mitsubishi Chemical Corporation, trade name) other ^{R 8} is a hydrogen atom, all the ^{R 8} are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, When all the R ^{8 s} are hydrogen atoms, or when the positions of the R ^{8 s} substituted by oxygen atoms are the 4 and 4'positions, the 3,3 ', 5,5' positions are methyl groups and the other R's are not. YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixed product in which ⁸ is a hydrogen atom, is commercially available.

In 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, and all may be the same or different. n is an average value and represents a number of 0 to 10.

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), 3,3 ′, 5,5 ′ positions are methyl groups when the oxygen atom-substituted position of R ⁹ is 4 and 4 ′ positions. And R ⁹ is a hydrogen atom other than the above, all of R ¹⁰ are hydrogen atoms, and three of the 3,3 ′, 5,5 ′ positions of R ⁹ are methyl groups, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixture with one of which is a t-butyl group, R ⁹ other than that is a hydrogen atom, and all R ¹⁰ are hydrogen atoms, It is available as a commercial product.

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

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and 3,3 when the positions of R ¹² substituted with oxygen atoms are 4 and 4 ′ positions. YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the ', 5, 5'position is a methyl group and the other R ¹² is a hydrogen atom is commercially available.

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

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) may be mentioned. Among the epoxy resins represented by the following general formula (V), 3,3'-position is t-butyl group when the position where the oxygen atom is substituted in R ¹³ is 4 and 4'-positions, YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the 6,6 ′ position is a methyl group and the other R ¹³ is a hydrogen atom is commercially available.

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

The novolac type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolac type phenol resin such as a phenol novolac resin, a cresol novolac resin, or a naphthol novolac resin using a method such as glycidyl etherification is preferable, and is represented by the following general formula (VI). Epoxy 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 name), all of R ¹⁴ are hydrogen atoms, and i = 0, N-770 and N-775 (DIC Corporation, trade name), all of R ¹⁴ are hydrogen atoms, and i = 0. YDAN-1000-10C (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), which is a styrene-modified phenol novolac type epoxy resin having a certain part and a part in which i = 1 and R ¹⁵ is —CH (CH ₃ ) -Ph. Benzyl having a moiety in which all of R ¹⁴ are hydrogen atoms, i = 1, a moiety in which R ¹⁵ is a methyl group and i = 2, and one of R ¹⁵ is a methyl group and one is a benzyl group Group-modified HP-5600 (DIC Corporation, trade name) is a Orres novolak type epoxy resin and the like are available as a commercial product.

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

  The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferable. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) having i = 0 and the like are commercially available.

In formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 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 etherifying a triphenylmethane type phenolic resin such as a novolak type phenolic 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). The epoxy resin used is more preferable. Among the epoxy resins represented by the following general formula (VIII), i = 0 and k = 01032H60 (Mitsubishi Chemical Co., Ltd., trade name), EPPN-502H (Nippon Kayaku Co., Ltd., trade name) Etc. are commercially available.

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

Copolymerization type epoxy resin obtained by epoxidizing a novolac 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 novolac type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name, in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0) ) Etc. are commercially available.

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

  As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 constitutional unit and m constitutional units at random, an alternating copolymer containing them alternately, a copolymer containing them regularly , Block copolymers contained in blocks, and the like. Any one of these may be used alone or in combination of two or more.

  The copolymer type epoxy resin is a methoxynaphthalene / cresol formaldehyde co-condensation type epoxy resin containing the following two types of structural units in random, alternating or block order, and is represented by the following general formula: Epicuron HP-5000 (DIC Co., Ltd., trade name) is also preferred. In the following general formula, n and m are each an average value, a number of 0 to 10, (n + m) represents a number of 0 to 10, preferably n and m are each an average value, and 1 to 9 And (n + m) is a number from 2 to 10.

  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. It is not particularly limited as long as it is an epoxy resin made from a 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. The epoxy resin obtained by glycidyl etherification is preferable, and the epoxy resins represented by the following general formulas (X) and (XI) are more preferable.

Among the epoxy resins represented by the following general formula (X), NC is 3000, in which i is 0 and R ³⁸ is a hydrogen atom (Nippon Kayaku Co., Ltd., trade name), i is 0, and R ^{38 is} CER-3000 (Nippon Kayaku Co., Ltd., trade name) in which an epoxy resin in which is a hydrogen atom and an epoxy resin in which all R ⁸ of the general formula (II) are hydrogen atoms are mixed at a mass ratio of 80:20 are commercially available. It is available as a product. Moreover, among the epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) having i = 0, j = 0 and k = 0 is commercially available. It is available as a product.

In formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all 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 of them 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 0-10 independently.

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} above general formulas (II) to (XI), “all may be the same or different” means, for example, ^{8 to} R in the formula (II). It means that all of 88 R ⁸ 's may be the same or different. It also means that all other R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same or different with respect to the respective numbers contained in the formula. Further, R ^{8 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same or different. For example, R ⁹ and R ¹⁰ may all 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 it is preferable that n is 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 of the epoxy resin composition at the time of melt molding lowers, filling failure, deformation of bonding wire (gold wire connecting element and lead), etc. Is likely to be suppressed. More preferably, n is set in the range of 0-4.

  Specific examples of preferred epoxy resins that can be used in the epoxy resin composition have been described above along the above general formulas (II) to (XI), but as more specific preferred epoxy resins, from the viewpoint of reflow resistance. , 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl, and 4,4′-bis (from the viewpoint of moldability and heat resistance. 2,3-epoxypropoxy) -biphenyl is mentioned.

  The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of various property balances such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and 150 g / eq to 500 g / eq. Is more preferable.

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

  The content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and 2% by mass to 30% by mass. More preferably.

(Phenolic curing agent)
The epoxy resin composition of the present disclosure contains a phenol curing agent. 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. Acid compounds and at least one phenolic compound selected from the group consisting of naphthol compounds such as phenol compounds and α-naphthol, β-naphthol, dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. Novolac type phenolic resin obtained by condensation or co-condensation under a catalyst; the above phenolic compound, dimethoxyparaxylene, bis (methoxy) Aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin synthesized from methyl) biphenyl and the like; paraxylylene and / or metaxylylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; 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; the above phenolic compound, benzaldehyde, 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, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, copolymer type phenol resin of benzaldehyde type phenol resin and aralkyl type phenol resin, and At least one selected from the group consisting of novolac type phenol resins (these are referred to as "specific phenol curing agents") is preferable. The specific phenol curing agents may be used alone or in combination of two or more.

  When the phenol curing agent contains the specific phenol curing agent, the content of the specific phenol curing agent is preferably 30% by mass or more, and 50% by mass or more of the entire phenol curing agent from the viewpoint of sufficiently exerting the performance thereof. Is more preferable.

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

  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, phenolic resins represented by the following general formulas (XII) to (XIV) are preferable.

In formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all 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, which may be the same or different. R ²⁶ and R ²⁷ represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and 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 p is each independently an integer of 0 to 4. is there. n is an average value and is a number of 0-10 independently.

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

  Among the phenolic resins represented by the above general formula (XIII), XL is 225 in which i is 0 and k is 0, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd., Trade name) etc. are available as commercial products.

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

  The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among phenolic resins represented by the following general formula (XV), DPP (i.e. Nippon Petrochemical Co., Ltd., trade name) having i = 0 is commercially available.

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

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

  Among phenol 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 represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is independently an integer of 0 to 3, and k is independently an integer of 0 to 4. n is an average value and is a number from 0 to 10.

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

  Among phenol resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., trade name) having i = 0, k = 0 and q = 0 is commercially available. It is available as a product.

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

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

Among phenolic resins represented by the following general formula (XVIII), i is 0 and R ³⁵ is Tamanor 758, 759 (Arakawa Chemical Industry Co., Ltd., trade name), HP-850N (Hitachi Chemical Co., Ltd.). Co., Ltd., product name) etc. are available as commercial products.

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

The “all may be the same or different” described for R ^{22 to} R ³⁶ in the general formulas (XII) to (XVIII) is, for example, all of the i R ²² 's 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 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 general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. When 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 also becomes low, and unfilling failure, deformation of bonding wire (gold wire connecting element and lead), etc. Less likely to occur. The average n in one molecule is preferably set in the range of 0 to 4.

  The hydroxyl equivalent of the phenol curing agent is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

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

  The equivalent ratio of the epoxy resin and the phenol curing agent, that is, the ratio of the number of hydroxyl groups in the phenol curing agent to the number of epoxy groups in the epoxy resin (the number of hydroxyl groups in the phenol curing agent / the number of epoxy groups in the epoxy resin) is not particularly limited. In order to reduce the amount of each unreacted component, the range is preferably set to 0.5 to 2.0, and more preferably set to 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

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

  From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, Tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl Tertiary phosphines such as phosphine, 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. A compound having an intramolecular polarization formed by adding a compound having a π bond such as a quinone compound or diazophenylmethane; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol , 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methyl Phenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethyl Ruphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4′-hydroxybiphenyl After reacting with a halogenated phenol compound such as, a compound having an intramolecular polarization obtained through a step of dehydrohalogenation; tetra-substituted phosphonium such as tetraphenylphosphonium, or a boron atom such as tetra-p-tolylborate Tetra-substituted phosphoniums and tetra-substituted borates without bound phenyl groups; salts of tetra-substituted phosphoniums with anions whose protons are desorbed from phenol compounds, salts of tetra-substituted phosphoniums with anions whose protons are desorbed from carboxylic acid compounds, etc. Is mentioned.

  Among the above phosphonium compounds, compounds represented by the following general formula (I-1) (hereinafter, also referred to as a specific curing accelerator) are preferable.

In formula (I-1), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. Alternatively, R ^{4 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁷ are bonded to each other to form a cyclic structure. You may form.

The “hydrocarbon group having 1 to 18 carbon atoms” described as R ^{1 to} R ^{3 in the} general formula (I-1) is an aliphatic hydrocarbon group having 1 to 18 carbon atoms and 6 to 18 carbon atoms. Contains certain aromatic hydrocarbon groups.

  From the viewpoint of fluidity, the aliphatic hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 4 to 6 carbon atoms.

  The aliphatic hydrocarbon group having 1 to 18 carbon atoms is an alicyclic hydrocarbon group having 3 to 18 carbon atoms, even if it is a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms. Good. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.

  Specific examples of the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, Examples thereof include an alkyl group such as a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group, an allyl group and a vinyl group. The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group and a t-butoxy group, an aryl group such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group and a halogen atom. The linear or branched aliphatic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18. From the viewpoint of curability, an unsubstituted alkyl group is preferable, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable, and an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. More preferred are groups.

  Specific examples of the alicyclic hydrocarbon having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group. The alicyclic hydrocarbon group may or may not have a substituent. As the substituent, an alkyl group such as a methyl group, an ethyl group, a butyl group, and a tert-butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a t-butoxy group, an aryl group such as a phenyl group, and a naphthyl group. , A hydroxyl group, an amino group, a halogen atom and the like. The alicyclic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3-18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of curability, an unsubstituted cycloalkyl group is preferable, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group, a cyclopentyl group and a cycloheptyl group are further preferable.

  The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. As the substituent, an alkyl group such as a methyl group, an ethyl group, a butyl group and a t-butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group and a t-butoxy group, an aryl group such as a phenyl group and a naphthyl group. , A hydroxyl group, an amino group, a halogen atom and the like. The aromatic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6-18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

  Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group and t-butyl. Examples thereof include a phenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group and a t-butoxyphenyl group. The position of the substituent in these aromatic hydrocarbon groups may be any of the ortho position, the meta position and the para position. From the viewpoint of fluidity, an unsubstituted aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including a substituent is preferable, and an unsubstituted aryl group having 6 to 10 carbon atoms or a carbon atom including a substituent. The aryl groups of the formulas 6 to 10 are more preferable, and the phenyl group, p-tolyl group and p-methoxyphenyl group are even more preferable.

The term “two or more of R ^{1 to} R ³ may be bonded to each other to form a cyclic structure” described as the description of R ^{1 to} R ^{3 in} the general formula (I-1) means R ^{1 to} R 3. ^It means a case where two or three of three are bonded to form one divalent or trivalent hydrocarbon group as a whole. Examples of R ^{1 to} R ^{3 in} this case include an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene that can be bonded to a phosphorus atom to form a cyclic structure, an alkenylene group such as ethylenylene, propylenylene, and butyrenylene group, Examples of the substituent include an aralkylene group such as a methylenephenylene group, an arylene group such as phenylene, naphthylene, and anthracenylene, and the like, which can bond to a phosphorus atom to form a cyclic structure. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom or the like.

The “organic group having 1 to 18 carbon atoms” described as R ^{4 to} R ^{7 in the} above general formula (I-1) has 1 to 18 carbon atoms, and may be substituted or unsubstituted. It is meant to include a group hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, an acyl group, a hydrocarbon oxycarbonyl group, and an acyloxy group.

Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group include those described above as examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group represented by R ^{1 to} R ³ .

  Examples of the aliphatic hydrocarbon oxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, t-butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group. , An oxy group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group such as an allyloxy group or a vinyloxy group, and these aliphatic hydrocarbon oxy groups are further an alkyl group, an alkoxy group, an aryl group, an aryloxy group, amino Examples thereof include those substituted with groups, hydroxyl groups, halogen atoms and the like.

  As the aromatic hydrocarbon oxy group, a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, an oxy having a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group such as a phenoxyphenoxy group. Groups, those in which these aromatic hydrocarbonoxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.

  Examples of the acyl group include an aliphatic hydrocarbon carbonyl group such as a formyl group, an acetyl group, an ethylcarbonyl group, a butyryl group, a cyclohexylcarbonyl group and an allylcarbonyl group, an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group and a methylphenylcarbonyl group. Etc., and the like in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms and the like.

  Examples of the hydrocarbon oxycarbonyl group include an methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an allyloxycarbonyl group, an aliphatic hydrocarbon oxycarbonyl group such as a cyclohexyloxycarbonyl group, a phenoxycarbonyl group, and a methylphenoxycarbonyl group. Aromatic hydrocarbon oxycarbonyl groups, these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. Things are included.

  Examples of the acyloxy group include an aliphatic hydrocarbon carbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group and a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group, a methylphenylcarbonyloxy group. And other aromatic hydrocarbon carbonyloxy groups, and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. Some of them have been made.

The term “two or more R ^{4 to} R ⁷ may be bonded to each other to form a cyclic structure” described as the description of R ^{4 to} R ^{7 in} the general formula (I-1) is 2 to 4 It means that R ^{4 to} R ⁷ are bonded to each other to form one divalent to tetravalent organic group as a whole. In this case, R ^{4 to} R ⁷ include alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene, alkenylene groups such as ethylenylene, propylenylene and butyrenylene, aralkylene groups such as methylenephenylene, arylene such as phenylene, naphthylene and anthracenylene. Examples of the substituent include a substituent capable of forming a cyclic structure such as a group, and an oxy group or a dioxy group thereof. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom or the like.

R ^{4 to} R ^{7 in the} general formula (I-1) are not particularly limited. For example, each may be independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. preferable. Among them, from the viewpoint of easy availability of raw materials, a hydrogen atom, a hydroxyl group, an unsubstituted or substituted aryl group with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a chain or cyclic alkyl group is preferable. Examples of the aryl group which is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include a phenyl group, a p-tolyl group, a m-tolyl group, an o-tolyl group and a p-methoxyphenyl group. Is mentioned. Examples of the chain or cyclic alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a t-butyl group, an octyl group and a cyclohexyl group. From the viewpoint of curability, it is preferable that R ^{4 to} R ⁷ are all hydrogen atoms, or that at least one of R ^{4 to} R ⁷ is a hydroxyl group and the rest are all hydrogen atoms.

In the general formula (I-1), more preferably, two or more of R ^{1 to} R ³ are an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, and R ^{4 to} R ⁷ are All are hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms. More preferably, all of R ^{1 to} R ³ are an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having ^{3 to} 18 carbon atoms, and R ^{4 to} R ⁷ are all hydrogen atoms, or at least one is a hydroxyl group. And the rest are all hydrogen atoms.

  From the viewpoint of fast curing property, the specific curing accelerator is preferably a compound represented by the following general formula (I-2).

In formula (I-2), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. Alternatively, R ^{4 to} R ⁶ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁶ are bonded to each other to form a cyclic structure. May be.

Specific examples of ^R 1 to R ⁶ in the formula (I-2) is the same as specific examples of ^R 1 to R ^6, respectively, in formula (I-1), and preferred ranges are also the same.

  Specific examples of the specific curing accelerator include addition reaction products of triphenylphosphine and 1,4-benzoquinone, addition reaction products of tri-n-butylphosphine and 1,4-benzoquinone, tricyclohexylphosphine and 1,4-benzoquinone. Addition reaction product, dicyclohexylphenylphosphine and 1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 1,4-benzoquinone addition reaction product, triisobutylphosphine and 1,4-benzoquinone addition reaction product, tricyclopentylphosphine And an addition reaction product of 1,4-benzoquinone.

The specific curing accelerator can be obtained, for example, as an adduct of a tertiary phosphine compound and a quinone compound.
Specific examples of the third phosphine compound include triphenylphosphine, 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, and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

  Specific examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferable.

The epoxy resin composition may contain a curing accelerator other than the phosphonium compound.
Specific examples of the curing accelerator other than the phosphonium compound include 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Cyclic amidine compounds such as diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; Phenol novolac salts of derivatives; maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-to these compounds Dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1, -Quinone compounds such as benzoquinone and phenyl-1,4-benzoquinone, compounds having an intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane; DBU tetraphenylborate salt, DBN tetraphenylborate Cyclic amidinium compounds such as salts, tetraphenylborate salts of 2-ethyl-4-methylimidazole, tetraphenylborate salts of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, Tertiary amine compounds such as tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate Examples thereof include ammonium, tetra-n-hexyl ammonium benzoate, and ammonium salt compounds such as tetrapropyl ammonium hydroxide.

  When the epoxy resin composition contains a specific curing accelerator as a curing accelerator, the content rate of the specific curing accelerator is preferably 30% by mass or more, and more preferably 50% by mass or more of the entire curing accelerator. It is preferably 70% by mass or more, and further preferably.

  The content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, and the total amount of the epoxy resin and the phenol curing agent (hereinafter, also referred to as “resin component”) is 100 parts by mass. The amount is preferably 0.1 parts by mass or more and less than 10 parts by mass, more preferably 0.3 parts by mass or more and less than 5 parts by mass. When the amount is 0.1 parts by mass or more, the composition can be cured in a short time, and when the amount is less than 10 parts by mass, the curing rate is not too fast, and a good molded product tends to be obtained.

(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 semiconductor packages, it is preferable to contain an inorganic filler.

  The type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite. Inorganic materials such as titania, talc, clay and mica can be mentioned. You may use the inorganic filler which has a flame retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, complex metal hydroxides such as complex hydroxide of magnesium and zinc, zinc borate and the like. Of these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic fillers may be used alone or in combination of two or more. Examples of the state of the inorganic filler include powder, beads made by spheroidizing the powder, and fibers.

  When the epoxy resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume of the entire epoxy resin composition, more preferably 35% by volume to 80% by volume, and 40% by volume to 70% by volume. It is more preferable that there is. When the content of the inorganic filler is 30% by volume or more based on the whole epoxy resin composition, properties such as thermal expansion coefficient, thermal conductivity and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire epoxy resin composition, the increase in viscosity of the epoxy resin composition is suppressed, the fluidity tends to be improved, and the moldability tends to be better. .

  The average particle size of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 50 μm, more preferably 0.5 μm to 30 μm. When the volume average particle diameter is 0.2 μm or more, increase in viscosity of the epoxy resin composition tends to be further suppressed. When the volume average particle diameter is 50 μm or less, the filling property into a narrow gap tends to be further improved. The volume average particle diameter of the inorganic filler can be measured as a volume average particle diameter (D50) by a laser diffraction / scattering particle size distribution measuring device.

  The volume average particle size of the inorganic filler in the epoxy resin composition or the cured product thereof can be measured by a known method. For example, the inorganic filler is extracted from the epoxy resin composition or the cured product using an organic solvent, nitric acid, aqua regia, etc., and sufficiently dispersed with an ultrasonic disperser or the like to prepare a dispersion liquid. Using this dispersion, the volume average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured by a laser diffraction / scattering particle size distribution analyzer. Alternatively, the volume average particle size of the inorganic filler should be measured from the volume-based particle size distribution obtained by observing the cross section obtained by embedding the cured product in a transparent epoxy resin or the like and polishing the cross section. You can Further, it is also possible to perform measurement by performing two-dimensional cross-section observation of the cured product continuously using a FIB device (focused ion beam SEM) and performing three-dimensional structural analysis.

  From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical rather than prismatic, and the particle size distribution of the inorganic filler is preferably widely distributed.

[Various additives]
The epoxy resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, and a stress relaxation agent, which are exemplified below, in addition to the above components. The epoxy resin composition may contain various additives well known in the art, if necessary, 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 epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane, titanium compounds, aluminum chelate compounds, aluminum / zirconium compounds. .

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

(Ion exchanger)
The epoxy resin composition may contain an ion exchanger. In particular, when the epoxy resin composition is used as a molding material for encapsulation, it is preferable to contain an ion exchanger from the viewpoint of improving the moisture resistance and the high temperature storage property of the electronic component device including the element to be encapsulated. . The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds, and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchangers may be used alone or in combination of two or more. 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, the content is not particularly limited as long as it is an amount sufficient to trap ions such as halogen ions. For example, it is preferably 0.1 parts by mass to 30 parts by mass and more preferably 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the resin component.

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

  When the epoxy resin composition contains a release agent, the content thereof is preferably 0.01 parts by mass to 15 parts by mass, and more preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin component. When the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold releasability tends to be sufficiently obtained. When it is 15 parts by mass or less, better adhesiveness tends to be obtained.

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

  When the epoxy resin composition contains a flame retardant, the content thereof is not particularly limited as long as it is an amount sufficient to obtain a desired flame retardant effect. For example, the amount is preferably 1 part by mass to 300 parts by mass, and more preferably 2 parts by mass to 150 parts by mass with respect to 100 parts by mass of the resin component.

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

(Stress relaxation agent)
The epoxy resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles. The inclusion of the stress relaxation agent can further reduce the warp deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include known stress relaxation agents (flexible agents) that are generally used. Specifically, thermoplastic elastomers such as silicone type, styrene type, olefin type, urethane type, polyester type, polyether type, polyamide type, polybutadiene type, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic Rubber, urethane rubber, rubber particles such as silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Examples thereof include rubber particles having a structure. The stress relaxation agent may be used alone or in combination of two or more. Of these, a silicone-based stress relaxation agent is preferable. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, those modified with polyether, and the like.

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

  The epoxy resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25 ° C. and atmospheric pressure). The shape of the solid epoxy resin composition is not particularly limited, and examples thereof include powder, granules, and tablets. From the viewpoint of handleability, it is preferable that the dimensions and weight of the epoxy resin composition in the form of a tablet be such that it meets the molding conditions of the package.

<Electronic component device>
An electronic component device according to an embodiment of the present disclosure includes an element sealed with the above-mentioned epoxy resin composition.
Examples of electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other supporting members, elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors). , A passive element such as a coil, etc.) and the element portion obtained by sealing the element portion with an epoxy resin composition.
More specifically, the element is fixed on a lead frame, the terminal portion of the element 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 Line Package), SOP (Small Outlet Lineage Package), SOJ (Small Outlet Lineage), and SOJ (Small Outlet Lineage). ), 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 supporting member by wire bonding, flip chip bonding, solder, etc. is sealed with an epoxy resin composition A COB (Chip On Board) module, a hybrid IC, a multi-chip module, etc .; an element is mounted on the surface of a supporting member having terminals for connecting a wiring board formed on the back surface, and the element and the supporting member are formed by bumping or wire bonding BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), and the like, which have a structure in which an element is sealed with an epoxy resin composition after connecting to the formed wiring. Further, the epoxy resin composition can also be preferably used in a printed wiring board.

  Examples of the method for sealing the electronic component device with 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 general.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited to these examples. In addition, "part" and "%" are based on mass unless otherwise specified.

[Preparation of epoxy resin composition]
Examples 1 to 12 and Comparative Examples 1 to 8 were prepared by mixing the following materials with the compositions (parts by mass) shown in Tables 1 and 2 and performing roll kneading under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes. The epoxy resin composition of was prepared.

(Epoxy resin)
Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (Mitsubishi Chemical Corporation, trade name “YX-4000H”)
Epoxy resin 2: Styrene-modified phenol novolac type epoxy resin having an epoxy equivalent of 282 and a softening point of 59 ° C. (Nippon Steel & Sumikin Chemical Co., Ltd., trade name “YDAN-1000-10C”)
Epoxy resin 3: methoxynaphthalene / cresol-formaldehyde co-condensation type epoxy resin having an epoxy equivalent of 250 and a softening point of 58 ° C. (DIC Corporation, trade name “HP-5000”)
Epoxy resin 4: Biphenylene skeleton-containing aralkyl type epoxy resin having an epoxy equivalent of 282 and a softening point of 56 ° C. (Nippon Kayaku Co., Ltd., trade name “NC-3000”)

(Curing agent)
Curing agent 1: Phenol aralkyl resin having a hydroxyl equivalent of 176 and a softening point of 70 ° C. (Meiwa Kasei Co., Ltd., trade name “MEH-7800”)
Hardener 2: Biphenyl skeleton type phenol aralkyl resin having a hydroxyl equivalent of 199 and a softening point of 89 ° C. (Meiwa Kasei Co., Ltd., trade name “MEH-7851”)

(Cyclic amide compound)
Cyclic amide compound 1; ε-caprolactam (Tokyo Kasei Kogyo Co., Ltd., reagent)
Cyclic amide compound 2; N-vinyl-ε-caprolactam (Tokyo Kasei Kogyo Co., Ltd., reagent)

(Curing accelerator)
Curing accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler)
Spherical fused silica (average particle size 17.5 μm, specific surface area 3.8 m ² / g)
(Coupling agent)
Epoxysilane (γ-glycidoxypropyltrimethoxysilane)
(Colorant)
Carbon black (Mitsubishi Chemical Corporation, trade name "MA-100")
(Release agent)
Carnauba wax

[Evaluation of epoxy resin composition]
The characteristics of the epoxy resin compositions produced in Examples 1 to 12 and Comparative Examples 1 to 8 were evaluated by the following characteristic tests. The evaluation results are shown in Tables 3 to 4 below. The epoxy resin composition was molded by a transfer molding machine at a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, unless otherwise specified. If necessary, post-curing was performed at 175 ° C. for 5 hours.

(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) Hardness at time of heat The epoxy resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D type hardness meter (HD-1120 (type D) manufactured by Kamijima Seisakusho Co., Ltd.) was used. It was measured using.

(3) 260 ° C. Elastic Modulus Measurement The epoxy resin composition was molded into a size of length 50 mm × width 5 mm × thickness 2 mm under the above conditions, and post-cured under the above conditions. Then, using a viscoelasticity measuring device RSA-3 (manufactured by TA Instruments Co., Ltd.), measurement was performed in a three-point bending mode under conditions of a temperature rising rate of 10 ° C./min and a frequency of 1 Hz. From the measurement result, the elastic modulus (GPa) at 260 ° C. was read.

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

(5) Reflow resistance
Epoxy is applied to a 80-pin flat package (QFP) (lead frame material: copper alloy, die pad upper surface and lead tip silver plated product) with an external dimension of 20 mm × 14 mm × 2 mm mounted with a 8 mm × 10 mm × 0.4 mm silicon chip. The resin composition was molded under the above conditions and post-cured under the above conditions. The obtained package was humidified at 85 ° C. and 85% RH for 168 hours. After that, reflow treatment is performed at a predetermined temperature (250 ° C., 260 ° C., 270 ° C.) for 10 seconds, and the presence or absence of cracks inside the package is visually inspected by an ultrasonic flaw detector (Hitachi). It was observed with Construction Machinery Co., Ltd., HYE-FOCUS). The reflow resistance was evaluated by the total number of packages in which either cracking or peeling occurred with respect to the number of test packages (10).

  As shown in Tables 3 to 4, when the epoxy resin compositions of Examples 1 to 12 containing the cyclic amide compounds 1 to 2 were used, elasticity at high temperature was higher than that of Comparative Examples 1 to 8 containing no cyclic amide compound. The rate tends to decrease, and the reflow resistance has improved.

Claims (6)

  An epoxy resin composition containing an epoxy resin, a phenol curing agent, and a cyclic amide compound.   The epoxy resin composition according to claim 1, wherein the cyclic amide compound contains at least one selected from the group consisting of ε-caprolactam and derivatives thereof.   The epoxy resin composition according to claim 1 or 2, wherein the content of the cyclic amide compound is 0.01% by mass to 10.0% by mass.   The epoxy resin composition according to any one of claims 1 to 3, further comprising a curing accelerator.   The epoxy resin composition according to any one of claims 1 to 4, further containing an inorganic filler.   An electronic component device comprising an element sealed with the epoxy resin composition according to claim 1.