JP2020063388A - Curable resin composition and electronic component device - Google Patents

Abstract

To provide a curable resin composition that makes it possible to obtain a sealing structure having excellent metal adhesiveness and reflow resistance, and an electronic component device obtained by using the same.SOLUTION: A curable resin composition contains an epoxy resin and a curing agent. The curing agent contains a phenol novolac resin containing a structural unit derived from a phenolic compound represented by general formula (1). In general formula (1), Ris a hydrogen atom or a methyl group, Ris a C10-18 aliphatic hydrocarbon group, n is an integer of 1 or 2.SELECTED DRAWING: None

Description

  The present invention relates to a curable 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 Integration).

  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, for example, 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, the method of using the epoxy group-containing silane coupling agent or the amino group-containing silane coupling agent may not have sufficient effect of improving the adhesiveness to the metal on the surface of the lead frame. Further, when the sulfur atom-containing silane coupling agent is used, there is a problem that the effect of improving the adhesiveness to a specific metal such as gold or silver is not sufficient.

  In view of the above circumstances, it is an object of the present invention to provide a curable resin composition capable of obtaining a sealing structure having excellent adhesion to metals and reflow resistance, and an electronic component device obtained by using the curable resin composition.

Means for solving the above problems include the following embodiments.
<1> A curable resin composition containing an epoxy resin and a curing agent, wherein the curing agent contains a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.)
<2> The phenol novolac resin is a phenol compound represented by the following general formula (1-1) to general formula (1-3) as a structural unit derived from the phenol compound represented by the general formula (1). The curable resin composition according to <1>, containing at least one structural unit derived from the curable resin composition.

(In the general formula (1-1) to formula (1-3), ^{R 2} has the same meaning as ^{R 2} in the general formula (1).)
<3> The curable resin composition according to <1> or <2>, wherein the phenol novolac resin further contains a structural unit derived from a phenol compound other than the phenol compound represented by the general formula (1).
<4> Any one of <1> to <3>, wherein the curing agent further contains a curing agent other than a phenol novolac resin containing a structural unit derived from the phenol compound represented by the general formula (1). The curable resin composition according to.
<5> The curable resin composition according to any one of <1> to <4>, which is used as a sealing material for an electronic component device.
An electronic component device comprising a <6> element and a cured product of the curable resin composition according to any one of <1> to <5>, which seals the element.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which can obtain the sealing structure excellent in adhesiveness with respect to metal, and reflow resistance, and the electronic component apparatus obtained using this are provided.

  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 term “process” includes not only a process independent of other processes but also the process even if the process is not clearly distinguishable from other processes as long as the purpose of the process is achieved. .
In the present disclosure, the numerical range indicated by using "to" includes 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. In the numerical range described, 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 means that when there are a plurality of substances corresponding to each component in the composition, the plurality of substances 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.

<Curable resin composition>
The curable resin composition of the present disclosure includes an epoxy resin and a curing agent, and the curing agent is a phenol novolac resin (hereinafter, a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1). Specific phenol novolac resin is also included).

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

  The curable resin composition containing the specific phenol novolac resin has excellent adhesiveness to a metal (in particular, gold) in a cured state. Although the reason is not clear, for example, an aliphatic hydrocarbon group having 10 to 18 carbon atoms contained in the structural unit derived from the phenol compound contained in the specific phenol novolac resin acts so as to improve adhesiveness to a metal. It is possible that Furthermore, the aliphatic hydrocarbon group having 10 to 18 carbon atoms contained in the structural unit derived from the phenol compound contained in the specific phenol novolac resin has a reduced elastic modulus in the vicinity of the interface between the metal surface and the cured product of the curable resin composition. It is considered that the reflow resistance is improved as a result of the action of reducing the water absorption rate.

  A curable resin composition containing a specific phenol novolac resin has excellent adhesiveness to a metal in a cured state, and therefore, an encapsulant for a package including a lead frame whose surface is at least a metal (in particular, gold). Is suitable as Examples of the lead frame having at least the surface material of gold include a lead frame obtained by plating a copper lead frame called PPF (Pre Plating Lead Flame) with Ni-Pd-Au plating.

(Specific phenol novolac resin)
The specific phenol novolac resin is a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1).

In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

  The structural units derived from the phenol compound represented by the general formula (1) contained in the specific phenol novolac resin may have the same structure or different from each other. When the specific phenol novolac resin contains two or more structural units derived from the phenol compound represented by the general formula (1), the arrangement of these is not particularly limited, and even if they are arranged regularly, they are arranged irregularly. May be done.

  In one embodiment, the specific phenol novolac resin has a structural unit (monohydric phenol) in which n is 1 and a structural unit in which n is 2 as a structural unit derived from the phenol compound represented by the general formula (1). Dihydric phenol), the structural unit (monohydric phenol) in which n is 1 and the structural unit in which n is 2 is a meta-position of one hydroxyl group to the other hydroxyl group. And the structural unit in 1) may be included.

  The specific phenol novolac resin is a structural unit derived from the phenol compound represented by the following general formula (1-1) to general formula (1-3) as a structural unit derived from the phenol compound represented by the general formula (1). At least one of the structural units derived from the phenol compound represented by the general formula (1-1) to the general formula (1-3) may be contained.

In the formula (1-1) to formula (1-3), ^{R 2} has the same meaning as ^{R 2} in the general formula (1).

In the general formula (1), the aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by R ² may be an aliphatic hydrocarbon group having 13 to 16 carbon atoms and has an unsaturated double bond. It may or may not have. When the aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by R ² has an unsaturated double bond, the number thereof is not particularly limited and may be 1 to 5, for example. The aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by R ² may be branched or unbranched, but is preferably unbranched. Specific examples of the aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by R ² include an aliphatic hydrocarbon group represented by the following group (A) (* indicates a bonding position with an aromatic ring). Can be mentioned. The structures of the aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by R ² in the specific phenol novolac resin may be the same or different.

  The specific phenol novolac resin may further include a structural unit derived from a phenol compound other than the phenol compound represented by the general formula (1). Examples of the phenol compound other than the phenol compound represented by the general formula (1) include a phenol compound represented by the following general formula (2).

In General Formula (2), R ¹ represents a hydrogen atom or a methyl group, and n is an integer of 1 or 2. Examples of the phenol compound represented by the general formula (2) include monohydric phenol compounds such as phenol and cresol, and dihydric phenol compounds such as resorcin, catechol and hydroquinone.

  In one embodiment, the specific phenol novolac resin may include one or both of phenol and cresol as a structural unit derived from the phenol compound represented by the general formula (2). Phenol and orthocresol One or both of the above may be included.

  When the specific phenol novolac resin contains a structural unit derived from a phenol compound other than the phenol compound represented by the general formula (1), the structural unit derived from the phenol compound represented by the general formula (1) is the specific phenol novolac resin. The proportion in the whole is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

  The method for synthesizing the specific phenol novolac resin is not particularly limited. For example, it can be synthesized by reacting a phenol compound as a raw material of a specific phenol novolac resin with an aldehyde such as formaldehyde in the presence of an acid catalyst.

  The molecular weight of the specific phenol novolac resin is not particularly limited. For example, the weight average molecular weight measured by gel permeation chromatography may be in the range of 300 to 20,000.

  The viscosity of the specific phenol novolac resin is not particularly limited. For example, the viscosity at 25 ° C. is preferably 50 Pa · s or less, more preferably 30 Pa · s or less. The viscosity of a specific phenol novolac resin at 25 ° C. is obtained by rotating an EHD type rotational viscometer equipped with a cone rotor having a cone angle of 3 ° and a cone radius of 14 mm at 25 ° C. for 1 minute and 10 times per minute (10 rpm). The value (Pa · s) is obtained by multiplying the measured value of 1 by a predetermined conversion coefficient (0.5).

  The hydroxyl equivalent of the specific phenol novolac resin 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 specific phenol novolac resin is preferably used in combination with a curing agent other than the specific phenol novolac resin. That is, the curable resin composition preferably contains a specific phenol novolac resin as a curing agent and a curing agent other than the specific phenol novolac resin.

  When the curable resin composition contains a specific phenol novolac resin as a curing agent and a curing agent other than the specific phenol novolac resin, from the viewpoint of curability, the proportion of the specific phenol novolac resin in the entire curing agent is equivalent. As a standard, it is preferably 50% or less, more preferably 30% or less, still more preferably 20% or less. From the viewpoint of improving the adhesion to metal, the proportion of the specific phenol novolac resin in the entire curing agent is preferably 1% or more, more preferably 3% or more, and more preferably 5% or more on an equivalent basis. Is more preferable.

  The type of curing agent other than the specific phenol novolac resin is not particularly limited, and can be selected according to the desired characteristics of the curable resin composition and the like. Specific examples of the curing agent will be described later.

(Epoxy resin)
The type of epoxy resin contained in the curable resin composition is not particularly limited and can be selected according to the desired characteristics of the curable resin composition and the like. Specific examples of the epoxy resin include at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolak type epoxy resin) which is an epoxidized novolak resin obtained by condensation or co-condensation of a certain phenolic compound with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Epoxy resin, orthocresol novolac type epoxy resin, etc.); The above phenolic compound and an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde are condensed or acid-catalyzed. Is a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by co-condensation; a novolak obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst. Copolymerization type epoxy resin obtained by epoxidizing resin; diphenylmethane type epoxy resin which is diglycidyl ether of bisphenol A, bisphenol F, etc .; biphenyl type epoxy resin which is diglycidyl ether of alkyl-substituted or unsubstituted biphenol; stilbene Stilbene type epoxy resin which is a diglycidyl ether of a phenolic compound; a sulfur atom-containing epoxy resin which is a diglycidyl ether of bisphenol S; butanediol, polyethylene glycol, polypropylene Epoxy resin which is a glycidyl ether of alcohols such as glycol; glycidyl ester type epoxy resin which is a glycidyl ester of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; nitrogen such as aniline, diaminodiphenylmethane and isocyanuric acid Glycidylamine type epoxy resin in which active hydrogen bonded to an atom is replaced with glycidyl group; dicyclopentadiene type epoxy resin in which cocondensation resin of dicyclopentadiene and phenol compound is epoxidized; intramolecular olefin bond Vinyl cyclohexene diepoxide, which is an epoxidized product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5, An alicyclic epoxy resin such as spiro (3,4-epoxy) cyclohexane-m-dioxane; a para-xylylene-modified epoxy resin which is a glycidyl ether of a para-xylylene-modified phenol resin; a meta-xylylene-modified epoxy resin which is a glycidyl ether of a meta-xylylene-modified phenol resin; Terpene-modified epoxy resin, which is a glycidyl ether of terpene-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin, which is a glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic Polycyclic aromatic ring modified epoxy resin which is glycidyl ether of aromatic ring modified phenolic resin; glycidyl ether of naphthalene ring containing phenolic resin Ether naphthalene 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; An aralkyl-type epoxy resin obtained by epoxidizing an aralkyl-type phenol resin such as a phenol aralkyl resin and 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, 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 crezo HP-5600 (DIC Corporation, trade name) is a novolac-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 a random, alternating or block order, which is represented by the following general formula, Epiclon HP-5000 ( DIC Corporation, 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 curable resin composition during melt molding decreases, the filling failure occurs, and the bonding wire (gold wire connecting the element and the lead) deforms. Occurrence of such a phenomenon tends to be suppressed. More preferably, n is set in the range of 0-4.

  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, it is preferably 40 ° C to 180 ° C, and more preferably 50 ° C to 130 ° C from the viewpoint of handleability during preparation of the curable resin composition.

  The content of the epoxy resin in the curable 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. Is more preferable.

(Curing agent other than specific phenol novolac resin)
The type of curing agent other than the specific phenol novolac resin contained in the curable resin composition is not particularly limited, and can be selected according to the type of epoxy resin used in combination, desired properties of the curable resin composition, and the like. Examples of the curing agent used in combination with the epoxy resin 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. From the viewpoint of compatibility between curability and pot life, at least one selected from the group consisting of phenol curing agents, amine curing agents and acid anhydride curing agents is preferable, and phenol curing agents are more preferable from the viewpoint of electrical reliability. 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. 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 phenol resin and dicyclopentadiene type naphthol resin synthesized by copolymerization with pentadiene; cyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin; biphenyl type phenol resin; the above phenolic compound and 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 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, based on the total amount of the curing agent, from the viewpoint of sufficiently exhibiting 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 further 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 curable resin composition at the time of melt molding also becomes low, and unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead) are prevented. 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 group equivalent in the case of a 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 curing agent 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 production of the curable resin composition, 50 ° C to 130 ° C is more preferable.

  The equivalent ratio of the epoxy 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 epoxy resin (the number of functional groups in the curing agent / the number of functional 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 curable 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 curable resin, desired properties of the curable 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-methylphenol , 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethyl Phenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4′-hydroxybiphenyl, etc. Compound having an intramolecular polarization, obtained by reacting the halogenated phenol compound of 1) with dehydrohalogenation, and bound to a tetra-substituted phosphonium such as tetraphenylphosphonium, or a boron atom such as tetra-p-tolylborate. A phenyl group-free tetra-substituted phosphonium and a tetra-substituted borate; a salt of a tetra-substituted phosphonium with an anion whose proton is eliminated from a phenol compound, a salt of a tetra-substituted phosphonium and an anion whose proton is eliminated from a carboxylic acid compound, etc. Can be 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 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 them are combined 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 R ^{4 to} R ^{7 in the} general formula (I-1) means 2 to 4 It means that R ^{4 to} R ⁷ may be combined 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 curable 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 curable 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 based on the entire curing accelerator. More preferably, it is more preferably 70% by mass or more.

  When the curable resin composition contains a curing accelerator, the amount thereof is preferably 0.1 parts by mass to 30 parts by mass and preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component. Is more preferable. When the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, the curing tends to be excellently performed in a short time. If the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing speed will not be too fast, and a good molded article will tend to be obtained.

(Inorganic filler)
The curable resin composition may include an inorganic filler. In particular, when the curable resin composition is used as a sealing material for semiconductor packages, it is preferable to include 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 non-powder, spherical beads, fibers and the like.

  When the curable resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, 30% by volume to 90% by volume of the entire curable resin composition is preferable, 35% by volume to 80% by volume is more preferable, and 40% by volume to 70% by volume. Is more preferable. When the content of the inorganic filler is 30% by volume or more of the entire curable resin composition, properties such as the 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 curable resin composition, the increase in viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better. It is in.

  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 10 μm, more preferably 0.5 μm to 5 μm. When the volume average particle diameter is 0.2 μm or more, increase in viscosity of the resin composition for mold underfill tends to be further suppressed. When the volume average particle diameter is 10 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 method particle size distribution measuring device.

  The volume average particle diameter of the inorganic filler in the curable resin composition or the cured product thereof can be measured by a known method. For example, the inorganic filler is extracted from the curable resin composition or the cured product using an organic solvent, nitric acid, aqua regia, or the like, and sufficiently dispersed with an ultrasonic disperser 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, measure the volume average particle size of the inorganic filler from the volume-based particle size distribution obtained by observing the cross section obtained by embedding the cured product in a transparent epoxy resin, etc. and polishing and observing with a scanning electron microscope. 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 fluidity of the curable 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 curable 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 curable resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.

(Coupling agent)
When the curable resin composition contains an inorganic filler, a coupling agent may be included 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 curable 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 curable resin composition may include an ion exchanger. In particular, when the curable resin composition is used as a molding material for encapsulation, it is preferable to include an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage property of an electronic component device including an 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 curable resin composition contains an ion exchanger, the content thereof 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 15 parts by mass with respect to 100 parts by mass of the resin component.

(Release agent)
The curable 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 curable resin composition contains a releasing agent, the amount thereof is preferably 0.01 parts by mass to 15 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, relative 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 curable resin composition may include 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 curable resin composition contains a flame retardant, the amount 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 curable resin composition may further include 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 curable resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By including the stress relaxation agent, it is possible to 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 curable resin composition)
The method for preparing the curable 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 curable resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25 ° C. and atmospheric pressure). The shape of the curable resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, and tablets. From the viewpoint of handleability, it is preferable that the size and weight of the curable 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 and a cured product of the curable resin composition that seals the element.
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) and an element portion obtained by mounting it with a curable resin composition.
More specifically, the element is fixed on a lead frame, and 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 transfer molding or the like using a curable resin composition. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outlet Line), and SOJ (Small Outlet Line). General resin encapsulation type IC such as Package), TQFP (Thin Quad Flat Package), etc .; TCP (Tape Carrier Package) having a structure sealed with a composition; a structure in which a wiring formed on a support member is connected to an element connected by wire bonding, flip chip bonding, solder, etc. with a curable 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), etc., which have a structure in which an element is sealed with a curable resin composition after connecting to the formed wiring. Further, the curable resin composition can also be suitably used in a printed wiring board.

  Examples of the method of sealing the electronic component device with the curable 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.

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

[Preparation of curable resin composition]
Examples 1 to 15 and Comparative Examples 1 to 1 were prepared by mixing the following materials with the compositions (parts by mass) shown in Tables 1 and 2 and performing roll kneading at a kneading temperature of 80 ° C. and a kneading time of 15 minutes. A curable resin composition of No. 8 was prepared.

(Epoxy resin)
Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 196 g / eq 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 g / eq and a softening point of 59 ° C. (Nippon Steel & Sumikin Chemical Co., Ltd., trade name “YDAN-1000-10C”)
Epoxy resin 3: methoxynaphthalene / cresol formaldehyde cocondensation type epoxy resin (DIC Corporation, trade name "HP-5000") having an epoxy equivalent of 250 g / eq and a softening point of 58 ° C.
Epoxy resin 4: Biphenylene skeleton-containing aralkyl type epoxy resin having an epoxy equivalent of 282 g / eq and a softening point of 56 ° C. (Nippon Kayaku Co., Ltd., trade name “NC-3000”)

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

(Curing agent of Examples)
Specific phenol novolac resin 1: industrial cashew nut shell liquid which is a mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A), and Novolak resin having a hydroxyl equivalent of 223 g / eq obtained by polycondensing phenol with formaldehyde and a viscosity at 25 ° C of 19.3 Pa · s (Gunei Chemical Industry Co., Ltd., trade name "ELP83H")
Specific phenol novolac resin 2: industrial cashew nut shell liquid, which is a mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A), Novolac resin having a hydroxyl equivalent of 209 g / eq obtained by polycondensing cresol and phenol with formaldehyde and a viscosity at 25 ° C of 14.0 Pa · s (Gunei Chemical Industry Co., Ltd., trade name "ELPC80").
Specific phenol novolac resin 3: industrial cashew nut shell liquid, which is a mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A), A novolak resin having a hydroxyl equivalent of 204 g / eq obtained by polycondensing cresol and phenol with formaldehyde and a viscosity at 25 ° C of 23.6 Pa · s (Gunei Chemical Industry Co., Ltd., trade name "ELPC75").
Specific phenol novolac resin 4: industrial cashew nut shell liquid which is a mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A), and Novolak resin with a hydroxyl equivalent of 204 g / eq obtained by polycondensing cresol with formaldehyde and a viscosity at 25 ° C of 20.2 Pa · s (Gunei Chemical Industry Co., Ltd., trade name "ELC75")

(Curing accelerator)
Curing accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler)
Spherical fused silica (volume average particle diameter 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 curable resin composition]
The characteristics of the curable resin compositions produced in Examples 1 to 15 and Comparative Examples 1 to 8 were evaluated by the following characteristic tests. The evaluation results are shown in Tables 3 and 4. The curable resin composition was molded by a transfer molding machine at a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, unless otherwise specified. If necessary, post-curing was performed at 175 ° C. for 5 hours.

(1) Spiral flow
The curable 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 upon heating 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), Ueshima Seisakusho Co., Ltd.) was used. It was measured using.

(3) 260 ° C shear adhesive strength
Under the above conditions, the curable resin composition was molded into a copper alloy plate (Pd-PPF) having a bottom surface diameter of 4 mm, a top surface diameter of 3 mm, and a height of 4 mm, and post-cured under the above conditions. Then, using a bond tester (Daiji Japan Co., Ltd., series 4000), the shear adhesive strength (MPa) was obtained at a shear rate of 50 μm / s while maintaining the temperature of the copper plate at 260 ° C.

(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. From the measurement results, the water absorption rate was calculated 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
An 80-pin flat package (QFP) (lead frame material: copper alloy (Pd-PPF)) with an external dimension of 20 mm × 14 mm × 2 mm, which is mounted with a silicon chip of 8 mm × 10 mm × 0.4 mm, is prepared by using a curable resin composition. And molded under the above conditions, and post-cured under the above conditions. The obtained package was humidified under conditions of 85 ° C. and 60% 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 Table 3 and Table 4, Examples 1 to 15 containing the specific phenol novolac resins 1 to 4 are more metal (Pd-PPF) than Comparative Examples 1 to 8 not containing the specific phenol novolac resin. Adhesion strength to and improved reflow resistance.

Claims (6)

A curable resin composition comprising an epoxy resin and a curing agent, the curing agent comprising a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.) Structure in which the phenol novolac resin is derived from a phenol compound represented by the following general formulas (1-1) to (1-3) as a structural unit derived from the phenol compound represented by the general formula (1) The curable resin composition according to claim 1, comprising at least one unit.

(In the general formula (1-1) to formula (1-3), ^{R 2} has the same meaning as ^{R 2} in the general formula (1).)   The curable resin composition according to claim 1 or 2, wherein the phenol novolac resin further contains a structural unit derived from a phenol compound other than the phenol compound represented by the general formula (1).   The curing agent according to any one of claims 1 to 3, wherein the curing agent further comprises a curing agent other than a phenol novolac resin containing a structural unit derived from the phenol compound represented by the general formula (1). Curable resin composition.   The curable resin composition according to claim 1, which is used as a sealing material for an electronic component device.   An electronic component device comprising: an element; and a cured product of the curable resin composition according to any one of claims 1 to 5, which seals the element.