JP2020045380A - Curable resin composition and electronic part device - Google Patents

Abstract

To provide a curable resin composition excellent in adhesion to metal in a cured state, and an electronic part device with an element sealed with the composition.SOLUTION: The curable resin composition comprises a curable resin and a compound represented by the general formula (1) in the figure. In the general formula (1), Rto Reach independently represent a monovalent hydrocarbon group, provided that one of Rto Rhas an epoxy group.SELECTED DRAWING: None

Description

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

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

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

  In order to meet the above demand, use of a silane coupling agent as a modifier for the inorganic filler contained in the sealing material has been studied. Specifically, use of an epoxy group-containing silane coupling agent or amino group-containing silane coupling agent (for example, see Patent Document 1), use of a sulfur atom-containing silane coupling agent (for example, see Patent Document 2), and the like. Are being considered.

  In order to meet the above demand, use of a silane coupling agent as a modifier for the inorganic filler contained in the sealing material has been studied. Specifically, use of an epoxy group-containing silane coupling agent or amino group-containing silane coupling agent (for example, see Patent Document 1), use of a sulfur atom-containing silane coupling agent (for example, see Patent Document 2), and the like. Are being considered.

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

  However, in the method using an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent, the effect of improving the adhesion of the lead frame surface to metal may not be sufficient. Further, when a silane coupling agent containing a sulfur atom is used, there is a problem that the effect of improving the adhesion to a noble metal such as gold is not sufficient.

  In view of the above circumstances, an object of the present invention is to provide a curable resin composition having excellent adhesion to metal in a cured state, and an electronic component device including an element sealed thereby.

Means for solving the above problems include the following embodiments.
<1> A curable resin composition containing a curable resin and a compound represented by the following general formula (1).

[In the general formula (1), R ^{1 to} R ³ each independently represent a monovalent hydrocarbon group, and ^one of R ^{1 to} R ³ has an epoxy group. ]

<2> The curable resin composition according to <1>, wherein at least one of R ^{1 to} R ³ in the general formula (1) is an allyl group.

<3> The curable resin composition according to <1> or <2>, further including an inorganic filler.

<4> The curable resin composition according to any one of <1> to <3>, wherein the curable resin contains an epoxy resin.

<5> The epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom containing type epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin. The curable resin composition according to <4>, comprising at least one selected from the group consisting of a polymerization type epoxy resin and an aralkyl type epoxy resin.

<6> The curable resin composition according to any one of <1> to <5>, further including a curing agent.

<7> The curing agent comprises an aralkyl phenol resin, a dicyclopentadiene phenol resin, a triphenylmethane phenol resin, a copolymer phenol resin of a benzaldehyde phenol resin and an aralkyl phenol resin, and a novolac phenol resin. The curable resin composition according to <6>, comprising at least one member selected from the group.

<8> The curable resin composition according to any one of <1> to <7>, further including a curing accelerator.

<9> The curable resin composition according to <8>, wherein the curing accelerator contains a phosphonium compound.

<10> The curable resin composition according to <8> or <9>, wherein the curing accelerator contains a compound represented by the following general formula (I-1).

[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. R ^{4 to} R ⁷ may be 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. May be formed. ]
<11> The curable resin composition according to <10>, wherein the compound represented by the general formula (I-1) includes 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. R ^{4 to} R ⁶ may be 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 may be bonded to each other to form a cyclic structure May be. ]
An electronic component device comprising: a <12>element; and a cured product of the curable resin composition according to any one of <1> to <11> for sealing the element.

  ADVANTAGE OF THE INVENTION According to this invention, the hardening resin composition which is excellent in the adhesiveness with respect to the metal in the hardened state, and an electronic component apparatus provided with the element sealed by this are provided.

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

In the present disclosure, the term "step" includes, in addition to a step independent of other steps, even if the purpose of the step is achieved even if it cannot be clearly distinguished from the other steps, the step is also included. .
In the present disclosure, the numerical ranges indicated by using “to” include the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described in stages 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 another numerical range described in stages. Further, in the numerical range described, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
In the present disclosure, the content or content of each component in the composition is, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the plurality of substances present in the composition Means the total content or content.
In the present disclosure, the particle diameter of each component in the composition, when there are a plurality of types of particles corresponding to each component in the composition, unless otherwise specified, for 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 embodiment contains a curable resin and a compound represented by the following general formula (1) (hereinafter, also referred to as a specific isocyanuric acid compound).
According to the study of the present inventors, the curable resin composition containing the specific isocyanuric acid compound has an adhesive property to a metal in a cured state (particularly, Pd-PPF (Palladium Pre Plated Leadframe) having gold in the outermost layer). It turned out to be excellent. Although the reason is not clear, it is presumed that the specific isocyanuric acid compound in the cured product forms a coordination bond with the metal.

  The curable resin composition containing the specific isocyanuric acid compound has excellent adhesiveness to gold in a cured state, and therefore, when used as a sealing material for a package including a lead frame in which at least the surface material is gold. Peeling between the lead frame and the sealing material is suppressed. Therefore, it has excellent reflow resistance.

(Specific isocyanuric acid compound)
The specific isocyanuric acid compound is a compound represented by the following general formula (1). As the specific isocyanuric acid compound, one kind may be used alone, or two or more kinds having different structures may be used in combination.

In the general formula (1), R ^{1 to} R ³ each independently represent a monovalent hydrocarbon group, and ^one of R ^{1 to} R ³ has an epoxy group.

The structure of the monovalent hydrocarbon group represented by R ^{1 to} R ³ is not particularly limited. For example, an aromatic hydrocarbon group and an aliphatic hydrocarbon group are mentioned.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, and an alicyclic hydrocarbon group having 3 to 18 carbon atoms.

  Specific examples of the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples 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.

  Specific examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, an adamantyl group, a norbornyl group, and a dicyclopentane. And the like.

The monovalent hydrocarbon group represented by R ^{1 to} R ³ may have a substituent other than the epoxy group. Examples of the substituent other than the epoxy group include an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an aromatic hydrocarbon. Examples include an amino group, an aliphatic hydrocarbon amino group, a diaromatic hydrocarbon amino group, a dialiphatic hydrocarbon amino group, and an aromatic hydrocarbon aliphatic hydrocarbon amino group.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, and an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
Examples of the aromatic hydrocarbon oxy group include those in which an oxygen atom is bonded to an aromatic hydrocarbon group such as a phenyl group and a naphthyl group.
As the aliphatic hydrocarbon oxy group, an oxygen atom is bonded to an aliphatic hydrocarbon group such as a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon having 3 to 18 carbon atoms. What was done.
Examples of the aromatic hydrocarbon amino group and the diaromatic hydrocarbon amino group include those in which an amino group is bonded to an aromatic hydrocarbon group such as a phenyl group and a naphthyl group.
Examples of the aliphatic hydrocarbon amino group and the dialiphatic hydrocarbon amino group include linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, and aliphatic aliphatic groups such as alicyclic hydrocarbons having 3 to 18 carbon atoms. Examples include those in which an amino group is bonded to a hydrocarbon group.
Examples of the aromatic hydrocarbon aliphatic hydrocarbon amino group include an aromatic hydrocarbon group such as a phenyl group and a naphthyl group and a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms and 3 to 18 carbon atoms. Examples thereof include those in which an amino group is bonded to an aliphatic hydrocarbon group such as an alicyclic hydrocarbon.

The carbon number of the monovalent hydrocarbon group represented by R ^{1 to} R ³ is not particularly limited. For example, each may independently have 1 to 30 carbon atoms, or 1 to 6 carbon atoms. When the monovalent hydrocarbon group represented by R ^{1 to} R ³ has a substituent, the carbon atoms contained in the substituent are also included in the “carbon number of the monovalent carbon atom”.

In one embodiment, ^one of R ^{1 to} R ³ is a monovalent hydrocarbon group having an epoxy group, and the other two are allyl groups. In some embodiments, ^one of R ^{1 to} R ³ is a glycidyl group and the other two are allyl groups. Specific examples of the specific isocyanuric acid compound include a compound having a structure represented by the following formula ( ^{one of} R ^{1 to} R ³ is a glycidyl group, and two of R ^{1 to} R ³ are an allyl group). No.

  The amount of the specific isocyanuric acid compound in the curable resin composition is not particularly limited. From the viewpoint of sufficiently obtaining the effect of improving the adhesiveness to gold and silver, for example, the total of the curable resin contained in the curable resin composition and the curing agent used as necessary (hereinafter, also referred to as “resin component”) ) The amount is preferably 0.5 parts by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more based on 100 parts by mass. From the viewpoint of curability, for example, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less based on 100 parts by mass of the resin component.

(Curable resin)
The curable resin is not particularly limited as long as it forms a three-dimensional crosslinked structure by a reaction, and may be thermosetting or photocurable. From the viewpoint of mass productivity, thermosetting is preferred. The curable resin may be one that is cured by self-polymerization or one that is cured by a reaction with a curing agent, a crosslinking agent, or the like.

  The functional group that causes the reaction of the curable resin is not particularly limited, and examples thereof include a cyclic ether group such as an epoxy group and an oxetanyl group, a hydroxyl group, a carboxy group, an amino group, an acryloyl group, an isocyanate group, a maleimide group, and an alkenyl group. From the viewpoint of the balance of properties as a sealing material, a curable resin containing a cyclic ether group is preferable, and a curable resin containing an epoxy group (epoxy resin) is more preferable.

When the curable resin is an epoxy resin, the type of the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
Specifically, at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak epoxy resin obtained by condensing or co-condensing an acidic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde and propionaldehyde under an acidic catalyst (phenol novolak epoxy resin, Orthocresol novolak type epoxy resin); obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane-type epoxy resin obtained by epoxidizing a triphenylmethane-type phenol resin obtained by epoxidizing a novolak resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound under an acidic catalyst. A diphenylmethane-type epoxy resin which is a diglycidyl ether of bisphenol A or bisphenol F; a biphenyl-type epoxy resin which is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a diglycidyl stilbene phenol compound Stilbene type epoxy resins which are ethers; sulfur atom-containing epoxy resins which are diglycidyl ethers such as bisphenol S; a such as butanediol, polyethylene glycol and polypropylene glycol. Epoxy resin which is a glycidyl ether of coals; Glycidyl ester type epoxy resin which is a glycidyl ester of polycarboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; Bonds to nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid Glycidylamine-type epoxy resin obtained by replacing activated hydrogen with a glycidyl group; dicyclopentadiene-type epoxy resin obtained by epoxidizing a cocondensation resin of dicyclopentadiene and a phenol compound; epoxidation of olefin bond in the molecule Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4 Epoxy) alicyclic epoxy resin such as cyclohexane-m-dioxane; paraxylylene-modified epoxy resin which is glycidyl ether of para-xylylene-modified phenol resin; meta-xylylene-modified epoxy resin which is glycidyl ether of meta-xylylene-modified phenol resin; glycidyl ether of terpene-modified phenol resin Terpene-modified epoxy resin; dicyclopentadiene-modified phenolic resin glycidyl ether; dicyclopentadiene-modified epoxy resin; glycidyl ether of cyclopentadiene-modified phenolic resin cyclopentadiene-modified epoxy resin; 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 novolak type epoxy resin; hydroquinone type epoxy resin; trimethylol propane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; phenol aralkyl resin Aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as naphthol aralkyl resins. Further, epoxidized products of silicone resin, epoxidized products of acrylic resin, and the like are also included as epoxy resins. These epoxy resins may be used alone or in combination of two or more.

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

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

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

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

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

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), when R ⁹ is substituted with an oxygen atom at positions 4 and 4 ′, the 3,3 ′, 5,5 ′ positions are methyl groups. R ⁹ is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3,3 ′, 5,5 ′ positions of R ⁹ are methyl groups, One is a t-butyl group, the other R ⁹ is a hydrogen atom, and all of R ¹⁰ are hydrogen atoms. It is available as a commercial product.

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

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

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

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

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

The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolak resin, a cresol novolak resin, and a naphthol novolak resin using a glycidyl etherification method 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 ^{R 14} is a hydrogen atom, N-770, N-775 is a i = 0 (DIC Corporation, trade ^name), all ^{R 14} is a hydrogen atom, with i = 0 A styrene-modified phenol novolak-type epoxy resin having a part where i = 1 and R ¹⁵ is —CH (CH ₃ ) —Ph, YDAN-1000-10C (Nippon Steel & Sumitomo Metal Corporation, trade name); All of R ¹⁴ are hydrogen atoms, i = 1, a portion in which R ¹⁵ is a methyl group and i = 2, and a benzyl having a portion in which 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 the formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i represents an integer of 0 to 3 each independently. n is an average value and shows the number of 0-10.

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

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

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

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

The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound and a phenol compound and an aldehyde compound is not particularly limited as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. . For example, an epoxy resin obtained by glycidyl etherification of a novolak type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Among the epoxy resins represented by the following general formula (IX), NC-7300 in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0 (Nippon Kayaku Co., Ltd., trade name) ) And the like are commercially available.

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

  Examples of the epoxy resin represented by the general formula (IX) include a random copolymer containing l constituent units and m constituent units at random, an alternating copolymer containing alternately, and a copolymer containing regularly. , Block copolymers and the like. Any one of these may be used alone, or two or more may be used in combination.

  As the copolymerizable epoxy resin, Epicron HP-5000 represented by the following general formula, which is a methoxynaphthalene-cresol formaldehyde co-condensation epoxy resin containing the following two types of structural units in random, alternating or block order: (DIC Corporation, trade name) is also preferred. In the following general formula, n and m are each an average value and a number of 0 to 10, and (n + m) indicates a number of 0 to 10. Preferably, n and m are each an average value, and 1 to 9 And (n + m) indicates a number of 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. The phenol resin is not particularly limited as long as it is an epoxy resin using phenol resin as a raw material. For example, a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or derivatives thereof Is preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

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

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

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

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

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

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

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

  The softening point of the curable resin is a value measured by a method according to JIS K 7234: 1986 (ring and ball method), and the melting point of the curable resin is a value measured by differential scanning calorimetry (DSC).

  The content of the curable resin in the curable resin composition is preferably 0.5% by mass to 50% by mass from the viewpoints of strength, fluidity, heat resistance, moldability, and the like, and is preferably 2% by mass to 30% by mass. % Is more preferable.

(Curing agent)
The curable resin composition may include a curing agent. The type of the curing agent is not particularly limited, and can be selected according to the type of the curable resin, desired characteristics of the curable resin composition, and the like.
When the curable resin is an epoxy resin, examples of the curing agent include 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. Can be From the viewpoint of compatibility between curability and pot life, at least one selected from the group consisting of a phenol curing agent, an amine curing agent and an acid anhydride curing agent is preferable, and from the viewpoint of electrical reliability, a phenol curing agent is more preferable. preferable.

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

  Among the phenol curing agents, from the viewpoint of reflow resistance, an aralkyl phenol resin, a dicyclopentadiene phenol resin, a triphenylmethane phenol resin, a copolymer phenol resin of a benzaldehyde phenol resin and an aralkyl phenol resin, and At least one selected from the group consisting of novolak-type phenol resins (these are referred to as “specific phenol curing agents”) is preferred. The specific phenol curing agent may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

  Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and k is 0 is commercially available.

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

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

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

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

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

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

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

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) means that, for example, all of i R ^{22 in} the formula (XII) are the same. However, it means that they may be different from each other. The other R ^{23 to} R ³⁶ also mean that all of the respective numbers included in the formula may be the same or different from each other. Further, R ^{22 to} R ³⁶ may be the same or different. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  N in the above general formulas (XII) to (XVIII) preferably ranges from 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the curable resin composition at the time of melt molding becomes low, and unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead) occur. Less likely to occur. The average n in one molecule is preferably set in the range of 0 to 4.

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

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

  The softening point or melting point of the curing agent is a value measured in the same manner as the softening point or melting point of the epoxy resin.

  The equivalent ratio between the curable resin and the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (the number of functional groups in the curing agent / the number of functional groups in the curable resin) is not particularly limited. From the viewpoint of minimizing the unreacted components, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the ratio in the range of 0.8 to 1.2.

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

  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 obtained 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 and the like A compound having an intramolecular polarization obtained through the step of dehydrohalogenation after reacting a halogenated phenol compound of formula (I) with a boron atom such as tetra-substituted phosphonium such as tetraphenylphosphonium or tetra-p-tolyl borate Tetra-substituted phosphonium and tetra-substituted borates without phenyl group; salts of tetra-substituted phosphonium with anions from which protons are eliminated from phenolic compounds; salts of tetra-substituted phosphonium with anions from which protons are eliminated from carboxylic acid compounds; No.

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

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. R ^{4 to} R ⁷ may be 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 may be bonded to each other to form a cyclic structure. It may be formed.

The “hydrocarbon group having 1 to 18 carbon atoms” described as R ^{1 to} R ^{3 in the} general formula (I-1) includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and a hydrocarbon group having 6 to 18 carbon atoms. Including certain aromatic hydrocarbon groups.
From the viewpoint of curability, at least one of R ^{1 to} R ^{3 in} the formula (I-1) is preferably an aliphatic hydrocarbon group having 1 to 18 carbon atoms, and two or more are preferably aliphatic hydrocarbon groups having 1 to 18 carbon atoms. Is more preferable, and all three are more preferably C1-C18 aliphatic 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 has 2 to 6 carbon atoms, and still more preferably has 4 to 6 carbon atoms.

  The aliphatic hydrocarbon group having 1 to 18 carbon atoms is a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, but is an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Is also good. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferable.

  Specific examples of the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, Examples 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 to 18. From the viewpoint of curability, an unsubstituted alkyl group is preferable, and an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable. An n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, and an n-octyl Groups are more preferred.

  Specific examples of the alicyclic hydrocarbon having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, and cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group. The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include 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, and 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 to 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 still more 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. Examples of the substituent include 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, and 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 to 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, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, and t-butyl. Examples 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, meta and para positions. From the viewpoint of fluidity, an unsubstituted aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including substituents is preferable, and an unsubstituted carbon group having 6 to 10 carbon atoms or carbon atoms including substituents. The aryl group having the number of 6 to 10 is more preferable, and a phenyl group, a p-tolyl group and a p-methoxyphenyl group are still more preferable.

The term “two or more of R ^{1 to} R ³ may combine with each other to form a cyclic structure” described as R ^{1 to} R ^{3 in the} general formula (I-1) means that R ^{1 to} R ³ Two or three of them combine 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, hexylene, etc., which can be combined with a phosphorus atom to form a cyclic structure; an alkenylene group such as ethylenylene, propylenylene, butyleneylene; Substituents such as an aralkylene group such as a methylenephenylene group and an arylene group such as phenylene, naphthylene and anthracenylene, which can form a cyclic structure by bonding to a phosphorus atom, are exemplified. 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} general formula (I-1) has 1 to 18 carbon atoms and may be substituted or unsubstituted. It includes an aromatic 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 a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a 2-butoxy group, a t-butoxy group, a cyclopropyloxy group, a cyclohexyloxy group, and a 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 and a vinyloxy group, and these aliphatic hydrocarbon oxy groups further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an amino group. And those substituted with a hydroxyl group, a halogen atom or the like.

  Examples of the aromatic hydrocarbon oxy group include phenoxy, methylphenoxy, ethylphenoxy, methoxyphenoxy, butoxyphenoxy, and phenoxyphenoxy groups, which have an oxygen atom bonded to the above aromatic hydrocarbon group. And 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, or 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; and an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group and a methylphenylcarbonyl group. And the like, in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

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

  Examples of the acyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group, an aliphatic hydrocarbon carbonyloxy group such as a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group, and a methylphenylcarbonyloxy group. Such as an aromatic hydrocarbon carbonyloxy group, such an aliphatic hydrocarbon carbonyloxy group or an aromatic hydrocarbon carbonyloxy group is further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like. And the like.

The term “two or more R ^{4 to} R ⁷ may combine with each other to form a cyclic structure” described as R ^{4 to} R ^{7 in the} above general formula (I-1) means that 2 to 4 It means that R ^{4 to} R ⁷ may combine 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 butyleneylene; aralkylene groups such as methylenephenylene; And 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 the availability of raw materials, a hydrogen atom, a hydroxyl group, an unsubstituted or at least one aryl group substituted 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 preferred. preferable. 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 includes a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-methoxyphenyl group and the like. 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 all of R ^{4 to} R ⁷ are 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 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 preferably 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 all of R ^{4 to} R ⁷ are hydrogen atoms, or at least one is a hydroxyl group. And the rest are all hydrogen atoms.

  From the viewpoint of quick curing, 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. R ^{4 to} R ⁶ may each independently be a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁶ may be bonded to each other to form a cyclic structure. You may.

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 an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, and tricyclohexylphosphine and 1,4-benzoquinone. Addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of triisobutylphosphine and 1,4-benzoquinone, tricyclopentylphosphine And 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, and 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 preferred.

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

The curable resin composition may contain other curing accelerators other than the phosphonium compound.
Other curing accelerators include diazabicyclo such as 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Cyclic amidine compounds such as alkenes, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or derivatives thereof Those compounds having maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl; -1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl Quinone compounds such as -1,4-benzoquinone, compounds having an intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane; tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, 2- Cyclic amidinium compounds such as tetraphenylborate salt of ethyl-4-methylimidazole and tetraphenylborate salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino) Tertiary amine compounds such as methyl) phenol; derivatives of the above tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n benzoate -Hexyl ammonium 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 of the specific curing accelerator is preferably 30% by mass or more of the entire curing accelerator, and more preferably 50% by mass or more. More preferably, it is even more preferably 70% by mass or more.

  When the curable resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, and preferably 1 to 15 parts by mass with respect to 100 parts by mass of the resin component. Is more preferred. When the amount of the curing accelerator is 0.1 parts by mass or more based on 100 parts by mass of the resin component, the curing tends to be performed well in a short time. If the amount of the curing accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, the curing rate tends to be too high and a good molded product tends 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 a semiconductor package, it is preferable to include an inorganic filler.

  The type of the inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite , Titania, talc, clay, mica and the like. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Among them, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One inorganic filler may be used alone, or two or more inorganic fillers may be used in combination. Examples of the state of the inorganic filler include non-powder, spherical beads and fibers, and the like.

  When the curable resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoints of fluidity and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, and more preferably 40% by volume to 70% by volume of the entire curable resin composition. 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 a thermal expansion coefficient, a thermal conductivity, and an 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, an increase in the viscosity of the curable resin composition is suppressed, and the flowability 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 from 0.2 μm to 10 μm, and more preferably from 0.5 μm to 5 μm. When the volume average particle diameter is 0.2 μm or more, an increase in the 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 narrow gaps 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 scattering diffraction particle size distribution analyzer.

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

  From the viewpoint of fluidity of the curable resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably wide.

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

[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 relaxing agent exemplified below, in addition to the above components. The curable resin composition may contain various additives known in the art as needed, in addition to the additives exemplified below.

(Coupling agent)
When the curable resin composition contains an inorganic filler, a coupling agent may be contained in order to enhance the adhesiveness between the resin component and the inorganic filler. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. .

  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 preferably 0.1 parts by mass to 100 parts by mass of the inorganic filler. More preferably, it is 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more based on 100 parts by mass of the inorganic filler, the adhesiveness to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion exchanger)
The curable resin composition may include an ion exchanger. In particular, when the curable resin composition is used as a molding material for sealing, it is preferable to include an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including the element to be sealed. . The ion exchanger is not particularly limited, and a conventionally known ion exchanger can be used. Specific examples include a hydrotalcite compound and a hydrated oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. One type of ion exchanger may be used alone, or two or more types may be used in combination. Among them, hydrotalcite represented by the following general formula (A) is preferable.

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

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

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

  When the curable resin composition contains a release agent, the amount is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the resin component. When the amount of the release agent is 0.01 part by mass or more based on 100 parts by mass of the resin component, there is a tendency that sufficient releasability is obtained. When the amount is 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 a conventionally known one can be used. Specifically, an organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, a metal hydroxide and the like can be mentioned. The flame retardants may be used alone or in combination of two or more.

  When the curable resin composition contains a flame retardant, its amount is not particularly limited as long as the amount is sufficient to obtain a desired flame retardant effect. For example, it is preferably from 1 to 300 parts by mass, more preferably from 2 to 150 parts by mass, per 100 parts by mass of the resin component.

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

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

(Preparation method of 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 of a predetermined compounding amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder, or the like, cooled, and pulverized. More specifically, for example, a method of uniformly stirring and mixing a predetermined amount of the above-mentioned components, kneading with a kneader, a roll, an extruder or the like which has been heated to 70 ° C. to 140 ° C., cooling, and pulverizing. Can be mentioned.

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

<Electronic component device>
An electronic component device according to an embodiment of the present disclosure includes an element and a cured product of the above-described curable resin composition that seals the element.
Electronic components include supporting elements such as lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, as well as elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, capacitors, and resistors). , A passive element such as a coil, etc.) is sealed with a curable resin composition.
More specifically, after fixing the element on a lead frame, connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding, bump or the like, and then performing transfer molding or the like using a curable resin composition. DIP (Dual Inline Package) having a sealed structure, PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package, SOJ (Small Outlet Package), SOJ (Small Outline Package) Package), TQFP (Thin Quad Flat Package), etc., general resin-sealed IC; TCP (Tape Carrier Package) having a structure sealed with a composition; a structure in which an element connected to a wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like is sealed with a curable resin composition. COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc. having an element; an element is mounted on a surface of a support member having terminals for wiring board connection formed on the back surface, and formed on the element and the support member by bump or wire bonding After the connection with the formed wiring, a ball grid array (BGA), a chip size package (CSP), a multi chip package (MCP), and the like having a structure in which the element is sealed with a curable resin composition are exemplified. Further, the curable resin composition can also be suitably used for a printed wiring board.

  Examples of a method for sealing an electronic component device using 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 common.

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

(Preparation of curable resin composition)
The following materials were mixed with the compositions (parts by mass) described in Tables 1 and 2, and kneading was carried out under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, whereby Examples 1 to 12 and Comparative Examples 1 to 9 were performed. Was prepared.

(Epoxy resin)
Epoxy resin 1: a 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 novolak-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: an aralkyl type epoxy resin containing a biphenylene skeleton 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”)
Curing agent 2: Biphenyl skeleton phenol aralkyl resin having a hydroxyl equivalent of 199 and a softening point of 89 ° C. (Meiwa Kasei Co., Ltd., trade name “MEH-7851”)

(Isocyanurate type epoxy compound)
Isocyanurate type epoxy compound 1; 1,3-diallyl-5-glycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd., trade name DA-MGIC)
Isocyanurate type epoxy compound A; 1-allyl-3,5-glycidyl isocyanurate (Shikoku Chemicals Co., Ltd., trade name MA-DGIC)

(Curing accelerator)
Curing accelerator: Addition 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 (Ceralica NODA)

[Evaluation of curable resin composition]
The properties of the curable resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 were evaluated by the following property tests. The evaluation results are shown in Tables 3 and 4 below. The curable resin composition was molded by a transfer molding machine at a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds unless otherwise specified. Post-curing was performed at 175 ° C. for 5 hours as needed.

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

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

(3) 260 ° C shear adhesive strength (Pd-PPF)
The curable resin composition was molded on a Pd-PPF-treated copper plate into the size of a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm under the above conditions, and post-cured under the above conditions. Thereafter, using a bond tester (Dage Japan Co., Ltd., Series 4000), the shear adhesive strength (MPa) was determined at a shear rate of 50 μm / s while maintaining the temperature of the copper plate at 260 ° C.

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

(5) Reflow resistance
Epoxy molding for molding 80 pin flat package (QFP) (lead frame material: copper alloy, Pd-PPF treated product) with external dimensions of 20 mm x 14 mm x 2 mm on which a silicon chip of 8 mm x 10 mm x 0.4 mm is mounted The material was molded under the above conditions and post-cured under the above conditions. The obtained package was humidified under the conditions of 85 ° C. and 60% RH for 168 hours. Thereafter, reflow treatment is performed at a predetermined temperature (250 ° C., 260 ° C., 270 ° C.) for 10 seconds, and the presence of cracks outside the package is visually observed. Construction Machine Co., Ltd., HYE-FOCUS). The reflow resistance was evaluated based on the total number of packages in which any of cracks and peeling occurred with respect to the number of test packages (10).

As shown in Tables 3 and 4, Examples 1 to 12 containing the isocyanurate type epoxy compound 1 corresponding to the specific isocyanuric acid compound showed a higher metal content than Comparative Examples 1 to 8 containing no isocyanurate type epoxy compound. The adhesion to Pd-PPF-treated copper) was improved, and the reflow resistance was also improved.
Comparative Example 9 containing the isocyanurate type epoxy compound A which does not correspond to the specific isocyanuric acid compound has a higher adhesive strength to metal (Pd-PPF treated copper) than Comparative Examples 1 to 8 which do not contain the isocyanurate type epoxy compound. No improvement in reflow resistance was observed.

Claims (12)

A curable resin composition comprising a curable resin and a compound represented by the following general formula (1).

[In the general formula (1), R ^{1 to} R ³ each independently represent a monovalent hydrocarbon group, and ^one of R ^{1 to} R ³ has an epoxy group. ] The curable resin composition according to claim 1, wherein at least one of R ^{1 to} R ³ in the general formula (1) is an allyl group.   The curable resin composition according to claim 1, further comprising an inorganic filler.   The curable resin composition according to any one of claims 1 to 3, wherein the curable resin includes an epoxy resin.   The epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom containing epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, a copolymer type epoxy resin The curable resin composition according to claim 4, comprising at least one selected from the group consisting of a resin and an aralkyl-type epoxy resin.   The curable resin composition according to any one of claims 1 to 5, further comprising a curing agent.   The curing agent is selected from the group consisting of an aralkyl phenol resin, a dicyclopentadiene phenol resin, a triphenylmethane phenol resin, a copolymer phenol resin of a benzaldehyde phenol resin and an aralkyl phenol resin, and a novolak phenol resin. The curable resin composition according to claim 6, which comprises at least one of the following.   The curable resin composition according to any one of claims 1 to 7, further comprising a curing accelerator.   The curable resin composition according to claim 8, wherein the curing accelerator contains a phosphonium compound. The curable resin composition according to claim 8, wherein the curing accelerator contains a compound represented by the following general formula (I-1).

[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. R ^{4 to} R ⁷ may be 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. May be formed. ] The curable resin composition according to claim 10, wherein the compound represented by the general formula (I-1) includes 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. R ^{4 to} R ⁶ may be 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 may be bonded to each other to form a cyclic structure May be. ]   An electronic component device comprising: an element; and a cured product of the curable resin composition according to claim 1, which seals the element.