KR20210019004A - Curable resin composition and electronic component device - Google Patents

Abstract

일반식 (1)에 있어서, R¹~R³은 각각 독립적으로 1가(價)의 탄화수소기를 나타낸다.A curable resin composition containing a curable resin and a compound represented by the following general formula (1).

In General Formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon group.

Description

Curable resin composition and electronic component device

[0001] The present invention relates to a curable resin composition and an electronic component device.

[0002] In recent years, according to the miniaturization, weight reduction, high performance, etc. of electronic devices, high-density of mounting is in progress. 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 integrated circuit (IC) or large scale integration (LSI).

[0003] A package of a surface mount type differs from a conventional pin insertion type and a mounting method. That is, when attaching a pin to a wiring board, in a conventional pin insertion type package, soldering is performed from the rear surface of the wiring board after inserting the pin into the wiring board, so that the package is not directly exposed to high temperatures. However, in a surface-mounted package, since the entire electronic component device is treated with 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 is moisture-absorbed, moisture due to moisture absorption rapidly expands during soldering, and the generated vapor pressure acts as a peeling stress, and between the inserts such as elements and lead frames and the sealing material. Peeling may occur, resulting in package cracks and poor electrical properties. For this reason, it is desired to develop a sealing material that is excellent in adhesion to an insert and, furthermore, excellent in solder heat resistance (reflow-resistant property).

[0004] In order to meet the above demands, the use of a silane coupling agent is being considered as a modifier for inorganic fillers included in the sealing material. Specifically, the use of an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent (for example, refer to Patent Document 1), and use of a sulfur atom-containing silane coupling agent (for example, refer to Patent Document 2) have been studied.

[0005] 1. Japanese Patent Laid-Open Publication No. H11-147939 2. Japanese Patent Laid-Open Publication No. 2000-103940

[0006] However, as a method of using an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent, the effect of improving the adhesion to metal on the surface of the lead frame may not be sufficient. In addition, when a sulfur atom-containing silane coupling agent is used, there is a problem that the effect of improving the adhesion to metals (especially noble metals such as gold and silver) is insufficient.

[0007] In view of the above circumstances, it is an object of the present invention to provide an electronic component device including a curable resin composition having excellent adhesion to metal in a cured state, and an element sealed thereby To

[0008] The following embodiments are included in the means for solving the above problems.

<1> Curable resin composition containing curable resin and a compound represented by following General formula (1).

[0009]

In General Formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon group.

<2> The curable resin composition according to <1>, wherein the compound represented by the general formula (1) contains a compound represented by the following general formula (2).

[0011]

[0012] In the general formula (2), R ⁴ to R ⁶ are each independently an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an aromatic hydrocarbon It is a monovalent group selected from the group consisting of 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. Each n is independently an integer of 0-5.

<3> The curable resin composition according to <2>, wherein at least one of R ⁴ to R ⁶ is a hydroxyl group.

<4> The curable resin composition according to any one of <1> to <3>, further comprising an inorganic filler.

<5> The curable resin composition according to any one of <1> to <4>, wherein the curable resin contains an epoxy resin.

<6> In <5>, the said 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 A curable resin composition comprising at least one selected from the group consisting of an epoxy resin, a triphenylmethane type epoxy resin, a copolymerization type epoxy resin, and an aralkyl type epoxy resin.

<7> The curable resin composition according to any one of <1> to <6>, further comprising a curing agent.

<8> In <7>, the curing agent is an aralkyl-type phenol resin, a dicyclopentadiene-type phenol resin, a triphenylmethane-type phenol resin, a benzaldehyde-type phenol resin and a copolymerization-type phenol resin of an aralkyl-type phenol resin, and novolac. Curable resin composition containing at least 1 type selected from the group consisting of type phenol resin.

<9> The curable resin composition according to any one of <1> to <8>, further comprising a curing accelerator.

<10> The curable resin composition according to <9>, wherein the curing accelerator contains a phosphonium compound.

The curable resin composition according to <11> <9> or <10>, wherein the curing accelerator contains a compound represented by the following general formula (I-1).

[0013]

[0014] 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 have a cyclic (環狀) structure May be formed, 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 may be bonded to each other to form a cyclic structure.

<12> The curable resin composition according to <11>, wherein the compound represented by the general formula (I-1) contains a compound represented by the following general formula (I-2).

[0015]

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 may be bonded to each other to form a cyclic structure. And 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 may be bonded to each other to form a cyclic structure.

An electronic component device comprising a <13> element and a cured product of the curable resin composition according to any one of <1> to <12> which seals the element.

[0017] According to the present invention, there is provided an electronic component device including a curable resin composition having excellent adhesion to metal in a cured state, and an element sealed thereby.

[0018] Hereinafter, an embodiment for carrying out the present invention will be described in detail. However, this invention is not limited to the following embodiment. In the following embodiments, the constituent elements (including urea steps, etc.) are not essential, except when specifically stated. The same applies to the numerical value and its range, and does not limit the present invention.

[0019] In the present disclosure, the term "process" includes, in addition to a process independent from other processes, if the purpose of the process is achieved, even if it cannot be clearly distinguished from other processes.

In the present disclosure, in the numerical range indicated by using "~", the numerical values described before and after "~" are included as minimum and maximum values, respectively.

In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be substituted with the upper limit value or the lower limit value of the numerical range described in another stepwise manner. In addition, in the numerical range described, the upper limit or lower limit of the numerical range may be substituted with a value shown in the examples.

In the present disclosure, the content rate or content of each component in the composition is the total content rate or content of the plurality of substances present in the composition, unless otherwise noted, when there are multiple types of substances corresponding to each component in the composition. Means.

In the present disclosure, the particle diameter of each component in the composition means a value related to a mixture of the plurality of particles present in the composition, unless specifically stated, when there are multiple types of particles corresponding to each component in the composition. do.

<Curable resin composition>

The curable resin composition which is one embodiment of the present disclosure contains a curable resin and a compound represented by the following general formula (1) (hereinafter, also referred to as a specific triazine compound).

According to the examination of the present inventors, it was found that the curable resin composition containing a specific triazine compound has excellent adhesion to metals (especially, noble metals such as gold and silver) in a cured state. The reason is not clear, but it is presumed to be because a specific triazine compound in the cured product forms a coordination bond with a metal.

[0021] Since the curable resin composition containing a specific triazine compound has excellent adhesion to metal in a cured state, at least when used as a sealing material for a package including a lead frame whose surface material is metal Peeling between the lead frame and the sealing material is suppressed. For this reason, it is excellent in reflow property.

[0022] (Specific triazine compounds)

A specific triazine compound is a compound represented by the following general formula (1). Specific triazine compounds may be used singly or two or more having different structures may be used.

[0023]

In General Formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon 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.

[0025] Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

As an aliphatic hydrocarbon group, a C1-C18 linear or branched aliphatic hydrocarbon group, a C3-C18 alicyclic hydrocarbon group, etc. are mentioned.

[0026] As a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, Alkyl groups, such as a hexyl group, an octyl group, a decyl group, and a dodecyl group, an allyl group, a vinyl group, etc. are mentioned.

[0027] As an alicyclic hydrocarbon group having 3 to 18 carbon atoms, specifically, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, and cyclohexenyl group, adamantyl group, norbornyl group, dicy Clofentanyl group, etc. are mentioned.

The monovalent hydrocarbon group represented by R ¹ to R ³ may have a substituent. As a substituent, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an aromatic hydrocarbon amino group, an aliphatic hydrocarbon amino group, a diaromatic hydrocarbon amino group, a dialiphatic hydrocarbon amino group, an aromatic hydrocarbon And aliphatic hydrocarbon amino groups.

[0029] 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.

Examples of the aliphatic hydrocarbon oxy group include those in which 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 group having 3 to 18 carbon atoms.

The number of carbon atoms in the monovalent hydrocarbon group represented by R ¹ to R ³ is not particularly limited. For example, each independently preferably has 1 to 30 carbon atoms. When the monovalent hydrocarbon group represented by R ¹ to R ³ has a substituent, the carbon atom included in the substituent is also included in "the number of carbon atoms of the monovalent carbon atom".

[0031] In certain embodiments, at least one of the monovalent hydrocarbon groups represented by R ¹ to R ³ is a phenyl group, and in another embodiment, all of the monovalent hydrocarbon groups represented by R ¹ to R ³ are phenyl groups. . The specific triazine compound may be a compound represented by the following general formula (2).

[0032]

[0033] In the general formula (2), R ⁴ to R ⁶ are each independently an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an aromatic hydrocarbon 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. n is each independently an integer of 0-5.

In the general formula (2), n may each independently be an integer of 1 to 3, or may be 2. In certain embodiments, at least one of R ⁴ to R ⁶ in General Formula (2) is a hydroxyl group.

In certain embodiments, in the specific triazine compound, one or two of R ¹ to R ³ in General Formula (1) is a 2,4-dimethylphenyl group. In another embodiment, two of R ¹ to R ³ are 2,4-dimethylphenyl group, and one is 2-hydroxy-4-n-octyloxyphenyl group. As a specific example of a specific triazine compound, a compound which has a structure represented by the following formula is mentioned.

[0036]

[0037] The amount of the specific triazine compound in the curable resin composition is not particularly limited. From the viewpoint of sufficiently obtaining the effect of improving adhesion to gold and silver, for example, per 100 parts by mass of the sum of the curable resin contained in the curable resin composition and the curing agent used as necessary (hereinafter also referred to as ``resin component'') It is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and even more preferably 3.0 parts by mass or more. From the viewpoint of curability, for example, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less based on 100 parts by mass of the resin component.

[0038] (curable resin)

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

[0039] The functional group that generates the reaction of the curable resin is not particularly limited, and includes a cyclic ether group such as an epoxy group, an oxetanyl group, a hydroxyl group, a carboxyl group, an amino group, an acryloyl group, an isocyanate group, a maleimide group, an alkenyl group, etc. Can be lifted. 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 (epoxy resin) containing an epoxy group is more preferable.

When the curable resin is an epoxy resin, the type of the epoxy resin is not particularly limited as long as it has two or more epoxy groups per molecule.

Specifically, 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. A novolac-type epoxy resin obtained by epoxidating a novolac resin obtained by condensation or co-condensation of at least one phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. (Phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, etc.); A triphenylmethane type epoxy resin obtained by epoxidating a triphenylmethane type phenol resin obtained by condensing or co-condensing the phenolic compound and an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst; A copolymerization type epoxy resin obtained by epoxidating a novolac resin obtained by co-condensing the phenol compound, naphthol compound, and an aldehyde compound under an acidic catalyst; Diphenylmethane type epoxy resins which are diglycidyl ethers such as bisphenol A and bisphenol F; Biphenyl-type epoxy resin which is a diglycidyl ether of alkyl substituted or unsubstituted biphenol; A stilbene type epoxy resin which is a diglycidyl ether of a stilbene phenol compound; Sulfur atom-containing epoxy resins such as diglycidyl ethers such as bisphenol S; Epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; Glycidyl ester type epoxy resins which are glycidyl esters of polyhydric carboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; A glycidylamine type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, and isocyanuric acid is substituted with a glycidyl group; A dicyclopentadiene type epoxy resin obtained by epoxidating a cocondensation resin of dicyclopentadiene and a phenol compound; Vinylcyclohexenediepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5 obtained by epoxidation of olefin bonds in the molecule Alicyclic epoxy resins such as ,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; Paraxylylene-modified epoxy resin, which is a glycidyl ether of a paraxylylene-modified phenol resin; Metaxylylene-modified epoxy resin, which is a glycidyl ether of metaxylylene-modified phenol resin; Terpene-modified epoxy resin which is 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 a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin which is glycidyl ether of polycyclic aromatic ring-modified phenol resin; Naphthalene type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; Halogenated phenol novolak type epoxy resin; Hydroquinone type epoxy resin; Trimethylolpropane type epoxy resin; Linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; An aralkyl type epoxy resin obtained by epoxidating an aralkyl type phenol resin such as a phenol aralkyl resin and a naphthol aralkyl resin; And the like. Furthermore, epoxidation products of silicone resin, epoxidation products of acrylic resin, etc. are also mentioned as an epoxy resin. These epoxy resins may be used singly or in combination of two or more.

[0041] Among the epoxy resins, from the viewpoint of balance of flowability and fluidity, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin , An epoxy resin selected from the group consisting of a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, a copolymerization type epoxy resin, and an aralkyl type epoxy resin (referred to as "specific epoxy resins") is preferable. Specific epoxy resins may be used singly or in combination of two or more.

When the epoxy resin contains a 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 total epoxy resin, and more preferably 50% by mass or more.

Among the specific epoxy resins, from the viewpoint of fluidity, a biphenyl-type epoxy resin, a stilbene-type epoxy resin, a diphenylmethane-type epoxy resin or a sulfur atom-containing epoxy resin is more preferable, and from the viewpoint of heat resistance, dish A clopentadiene type epoxy resin, a triphenylmethane type epoxy resin, or an aralkyl type epoxy resin is preferable. Hereinafter, a specific example of a preferable epoxy resin is 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. Among the epoxy resins represented by the following general formula (II), the 3,3', 5,5' positions when the positions where the oxygen atom is substituted in R ⁸ are the 4 and 4'positions are methyl groups, and other R ⁸ If this YX-4000H (Mitsubishi Chemical Corporation, trade names), all of R ⁸ is a 4,4-bis (2,3-epoxypropoxy) biphenyl, R ⁸ all are hydrogen atom and hydrogen atom, hydrogen atom, R YL-6121H (Mitsubishi) (Mitsubishi) is a mixed product in the case where the positions 3,3',5,5' are methyl groups and other R ⁸ is a hydrogen atom when the position where the oxygen atom is substituted among ⁸ is the 4 and 4'position. Chemical Corporation, brand name) etc. are available as a commercial item.

[0045]

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, each of which may be the same or different. n is an average value and represents 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), the 3,3', 5,5' positions when the oxygen atom is substituted in the 4 and 4'positions in R ⁹ are methyl groups, and other R ⁹ is a hydrogen atom, and when all of R ¹⁰ are hydrogen atoms, 3 of the 3,3',5,5' positions of R ⁹ are methyl groups, 1 is a t-butyl group, and other R ⁹ are hydrogen ESLV-210 (Sumitomo Chemical Company, Limited, brand name), which is an atom and a mixed product in which all of R ¹⁰ are hydrogen atoms, can be obtained as a commercial product.

[0048]

In formula (III), R ⁹ and R ¹⁰ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. n is an average value and represents 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 the 3,3', 5,5' positions when the positions where the oxygen atoms are substituted in R ¹² are the 4 and 4'positions. Is a methyl group, and YSLV-80XY (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name) etc. in which R ¹² is a hydrogen atom other than that can be obtained as a commercial item.

[0051]

In Formula (IV), R ¹¹ and R ¹² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. n is an average value and represents 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, the epoxy resin represented by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the 3,3' position when the position where the oxygen atom is substituted in R ¹³ is the 4 and 4'position is a t-butyl group, and the 6,6' position is YSLV-120TE (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name) etc., which is a methyl group and R ¹³ other than that is a hydrogen atom, can be obtained as a commercial item.

[0054]

In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. n is an average value and represents 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 novolac-type phenol resin. For example, an epoxy resin obtained by epoxidating a novolac-type phenol resin such as a phenol novolak resin, a cresol novolak resin, or a naphthol novolak resin using a method such as glycidyl etherification is preferred, and the following general formula (VI The epoxy resin represented by) is more preferable. Among the epoxy resins represented by the following general formula (VI), all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, i = 1 ESCN-190, ESCN-195 (Sumitomo Chemical Company, Limited, brand name), R ¹⁴ All are hydrogen atoms, i=0 N-770, N-775 (DIC Corporation, brand name), R ¹⁴ are all hydrogen atoms, i=0 and i=1, R ¹⁵ is -CH(CH ₃ ) YDAN-1000-10C (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name), a styrene-modified phenol novolak-type epoxy resin having a moiety of -Ph, all of R ¹⁴ are hydrogen atoms, i=1, and R HP-5600 (DIC Corporation, brand name), a benzyl group-modified cresol novolak-type epoxy resin having a moiety in which ¹⁵ is a methyl group and a moiety in which i=2, and one of R ¹⁵ is a methyl group and one is a benzyl group is available as a commercial item Do.

[0057]

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

The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidation using 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), i=0 HP-7200 (DIC Corporation, brand name) or the like can be obtained as a commercial item.

[0060]

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

The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin containing 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 novolac-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and the following general formula (VIII) The epoxy resin represented by is more preferable. Among the epoxy resins represented by the following general formula (VIII), 1032H60 in which i is 0 and k is 0 (Mitsubishi Chemical Corporation, brand name), EPPN-502H (Nippon Kayaku Co., Ltd., brand name) and the like are available as commercial products. It is possible.

[0063]

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

The copolymerized epoxy resin obtained by epoxidating a naphthol compound and a phenol compound and a novolak resin obtained from an aldehyde compound is not particularly limited as long as it is an epoxy resin containing 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., brand name) in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0 is a commercial item. Available.

[0066]

In the formula (IX), R ¹⁹ to R ²¹ represent a monovalent organic group having 1 to 18 carbon atoms, and each 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, and k is each independently an integer of 0 to 4. Each of l and m is an average value, is a number of 0-10, and (l+m) represents a number of 0-10. The terminal of the epoxy resin represented by formula (IX) is either of the following formula (IX-1) or (IX-2). In the formula (IX-1) and ^{(IX-2), R 19} ~ R 21 is defined in the i, j and k in the formula (IX) R ¹⁹ ~ R ²¹ is, for i, j, and k Same as definition. n is 1 (when bonded through a methylene group) or 0 (when not bonded through a methylene group).

[0068]

[0069] As the epoxy resin represented by the general formula (IX), a random copolymer containing l constituent units and m constituent units randomly, an alternating copolymer containing alternately, and regularly containing Copolymers, block copolymers included in a block form, and the like. Any one of these may be used alone, or two or more may be used in combination.

[0070] As a copolymerization type epoxy resin, Epiclon HP represented by the following general formula, which is a methoxynaphthalene-cresolformaldehyde cocondensation type epoxy resin comprising the following two types of structural units in random, alternating or block order -5000 (DIC Corporation, trade name) is also preferred. In the following general formula, n and m are each an average value, and is a number of 0-10, (n+m) represents a number of 0-10, preferably n and m are each average value, and is a number of 1-9, (n+m) represents the number of 2-10.

[0071]

Aralkyl-type epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethyl naphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or It does not specifically limit as long as it is an epoxy resin which uses a phenol resin synthesized from these derivatives as a raw material. For example, phenols 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 dimethyl naphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof The epoxy resin obtained by converting the resin into glycidyl ether is preferable, and the epoxy resin represented by the following general formulas (X) and (XI) is more preferable.

Among the epoxy resins represented by the following general formula (X), i is 0, R ³⁸ is a hydrogen atom, NC-3000S (Nippon Kayaku Co., Ltd., brand name), i is 0, and R ³⁸ is CER-3000 (Nippon Kayaku Co., Ltd., brand name) etc. obtained by mixing an epoxy resin as a hydrogen atom and an epoxy resin in which all R ^{8 in} the general formula (II) is a hydrogen atom in a mass ratio of 80:20 can be obtained as a commercial item. . In addition, among the epoxy resins represented by the following general formula (XI), ESN-175 (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name) in which i is 0, j is 0, and k is 0 is obtained as a commercial item. It is possible.

[0074]

In formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. R ³⁷ and R ³⁹ to R ⁴¹ represent a monovalent organic group having 1 to 18 carbon atoms, and each 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 each independently represents an integer of 0 to 6. n is an average value, and is a number of 0-10 each independently.

[0076] For R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ in the general formulas (II) to (XI), "each may be the same or different" means, for example, 8 to 88 in formula (II). It means that all of the R ^{8 of the} dog may be the same or different. Also for other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ , it means that all may be the same or different for each number included in the formula. In addition, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different. For example, both of R ⁹ and R ¹⁰ may be the same or different.

In addition, the organic group having 1 to 18 carbon atoms in General Formulas (III) to (XI) is preferably an alkyl group or an aryl group.

In the general formulas (II) to (XI), n is an average value, and it is preferable that each independently ranges from 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity at the time of melt molding of the curable resin composition decreases, resulting in poor filling, deformation of the bonding wire (gold wire connecting the element and the lead), etc. Tends to be suppressed. It is more preferable that n is set in the range of 0-4.

[0078] The functional group equivalent of the curable resin (in the case of an epoxy resin, the epoxy equivalent) is not particularly limited. From the viewpoint of balance of various properties such as moldability, reflowability, and electrical reliability, the functional group equivalent of the curable resin is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq. .

The softening point or melting point of the curable resin is not particularly limited. From the viewpoint of moldability and reflowability, it is preferably from 40°C to 180°C, and more preferably from 50°C to 130°C from the viewpoint of handling properties during preparation of the curable resin composition.

[0080] The content rate of the curable resin in the curable resin composition is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass from the viewpoint of strength, fluidity, heat resistance, and moldability. Do.

[0081] (hardener)

The curable resin composition may contain a curing agent. The type of curing agent is not particularly limited, and may be selected depending on the type of curable resin, desired properties of the curable resin composition, and the like.

Examples of the curing agent in the case where the curable resin is an 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 block isocyanate curing agent. From the viewpoint of both 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 a phenol curing agent is more preferable from the viewpoint of electrical reliability.

As the phenol curing agent, for example, a phenol resin having two or more phenolic hydroxyl groups per molecule, and a polyhydric phenol compound. Specifically, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; From the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene A novolak-type phenol resin obtained by condensing or co-condensing at least one selected phenolic compound and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; Aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin synthesized from the phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like; Para-xylylene and/or metaxylylene-modified phenolic resins; Melamine-modified phenolic resin; Terpene-modified phenolic resin; Dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol resin synthesized by copolymerization from the phenolic compound and dicyclopentadiene; Cyclopentadiene-modified phenol resin; Polycyclic aromatic ring modified phenol resin; Biphenyl type phenol resin; Triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenolic compound and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; And phenol resins obtained by copolymerizing two or more of these. These phenol curing agents may be used singly or in combination of two or more.

Among the phenol curing agents, from the viewpoint of reflowability, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, a benzaldehyde type phenol resin and an aralkyl type phenol resin copolymerized phenol resin, and a furnace At least one type selected from the group consisting of rockfish-type phenol resins (referred to as "specific phenol curing agents") is preferable. Specific phenol curing agents may be used singly or in combination of two or more.

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

Examples of the aralkyl-type phenol resin include a phenolic compound, a phenol aralkyl resin synthesized from dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like, and a naphthol aralkyl resin. The aralkyl-type phenol resin may be further copolymerized with other phenol resins. Examples of the copolymerized aralkyl-type phenol resin include a benzaldehyde-type phenolic resin and an aralkyl-type phenolic resin, a salicylaldehyde-type phenolic resin and an aralkyl-type phenolic resin, a novolak-type phenolic resin and an aralkyl-type phenolic resin. Copolymerization type phenol resin etc. are mentioned.

Aralkyl-type phenolic resin is particularly limited if it is a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof It doesn't work. For example, a phenol resin represented by the following general formulas (XII) to (XIV) is preferable.

[0087]

In formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each of them may be the same or different. R ²² , R ²⁴ , R ²⁵ and R ²⁸ represent a monovalent organic group having 1 to 18 carbon atoms, and each of them 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 each 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 p is each independently an integer of 0 to 4. n is an average value, and is a number of 0-10 each independently.

Among the phenolic resins represented by the general formula (XII), MEH-7851 (MEIWA PLASTIC INDUSTRIES, LTD., brand name) in which i is 0 and R ²³ is all hydrogen atoms can be obtained as a commercial item.

Among the phenolic resins represented by the general formula (XIII), i is 0, k is 0, XL-225, XLC (Mitsui Chemicals, Inc., brand name), MEH-7800 (MEIWA PLASTIC INDUSTRIES, LTD. , Brand name) and the like can be obtained as a commercial item.

Among the phenolic resins represented by the general formula (XIV), j is 0, k is 0, and p is 0, SN-170 (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name), j is 0 , K is 1, R ²⁷ is a hydroxyl group, p is 0, SN-395 (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name) etc. can be obtained as a commercial item.

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 the phenol resins represented by the following general formula (XV), DPP (Nippon Petrochemicals Co., Ltd., brand name) in which i is 0 can be obtained as a commercial item.

[0093]

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

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

Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (MEIWA PLASTIC INDUSTRIES, LTD., brand name) in which i is 0 and k is 0 is available as a commercial item.

[0097]

In Formula (XVI), R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 18 carbon atoms, and each of them 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 of 0-10.

The copolymerized phenolic resin of a benzaldehyde-type phenolic resin and an aralkyl-type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of a phenolic resin and an 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 phenol resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Inc., brand name) in which i is 0, k is 0, and q is 0 can be obtained as a commercial item.

[0101]

In Formula (XVII), R ³² to R ³⁴ represent a monovalent organic group having 1 to 18 carbon atoms, and each of them 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 each independently is a number of 0-11. However, the sum of l 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, and an aldehyde compound under an acidic catalyst. For example, a phenol resin represented by the following general formula (XVIII) is preferable.

Among the phenolic resins represented by the following general formula (XVIII), tamanol 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (HITACHI CHEMICAL), in which i is 0 and R ³⁵ is all hydrogen atoms. COMPANY, LTD., brand name) and the like can be obtained as a commercial item.

[0105]

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

[0107] "Each of R ²² to R ³⁶ in General Formulas (XII) to (XVIII) may be the same or different from each other". For example, all of i R ²² in Formula (XII) It means that they may be the same or different from each other. Also for the other R ²³ to R ³⁶ , it means that all may be the same or different from each other for each number included in the formula. In addition, R ²² to R ³⁶ may be the same or different. For example, both R ²² and R ²³ may be the same or different, and both R ³⁰ and R ³¹ may be the same or different.

It is preferable that n in the general formulas (XII) to (XVIII) is in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the curable resin composition is also lowered, and it is difficult to cause unfilling failure or deformation of the bonding wire (the gold wire connecting the element and the lead). It is preferable that the average n in 1 molecule is set in the range of 0-4.

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

[0110] The softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflowability, it is preferably from 40°C to 180°C, and more preferably from 50°C to 130°C from the viewpoint of handling properties in production of the curable resin composition.

The equivalent ratio of the curable resin and the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (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 suppressing each unreacted component to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflowability, it is more preferable to set it in the range of 0.8 to 1.2.

[0112] (hardening accelerator)

The curable resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited, and may 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. Specifically as a phosphonium compound, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl·alkoxyphenyl)phosphine, tris (Dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl) Tertiary phosphines such as phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naph Toquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone , A compound having intramolecular polarization obtained by adding a quinone compound such as phenyl-1,4-benzoquinone and a compound having a π bond such as diazophenylmethane; The tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodide phenol, 3 -Iodide phenol, 2-iodide phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5- Dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo- A compound having intramolecular polarization obtained by reacting a halogenated phenol compound such as 4'-hydroxybiphenyl and then through a step of dehalogenated hydrogen; Tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-substituted phosphonium and tetra-substituted borate without a phenyl group bonded to a boron atom such as tetra-p-tolylborate; A salt of a tetra-substituted phosphonium and an anion from which a proton has been removed from a phenol compound, a salt of a tetra-substituted phosphonium and an anion from which a proton has been released from a carboxylic acid compound, and the like.

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

[0115]

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 may be bonded to each other to form a cyclic structure. And 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 may be bonded to each other to form a cyclic structure.

[0117] 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 an aromatic hydrocarbon group having 6 to 18 carbon atoms do.

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

The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of production, it is preferably a linear or branched aliphatic hydrocarbon group.

[0120] As a straight-chain or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, Alkyl groups, such as a hexyl group, an octyl group, a decyl group, and a dodecyl group, an allyl group, a vinyl group, etc. are mentioned. Even if a linear or branched aliphatic hydrocarbon group has a substituent, it is not necessary to have it. 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, and the substituents in that case may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, it is preferable that the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is 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, and an n-butyl group, isobutyl group, n-pentyl group, n-hexyl group and The n-octyl group is 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. Even if the alicyclic hydrocarbon group has a substituent, it is not necessary to have it. Examples of the substituent include alkyl groups such as methyl, ethyl, butyl, and tert-butyl groups, alkoxy groups such as methoxy groups, ethoxy groups, butoxy groups, and t-butoxy groups, aryl groups such as phenyl groups and naphthyl groups, hydroxyl groups, amino groups, and halogens. Atom, etc. are mentioned. The alicyclic hydrocarbon group may have two or more substituents, and the substituents in that case may be the same or different. When the alicyclic hydrocarbon group has a substituent, it is preferable that the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is 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, a C4-10 unsubstituted cycloalkyl group 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 is preferably 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 alkyl groups such as methyl, ethyl, butyl, and t-butyl groups, alkoxy groups such as methoxy groups, ethoxy groups, butoxy groups, and t-butoxy groups, aryl groups such as phenyl groups and naphthyl groups, hydroxyl groups, amino groups, and halogens. Atom, etc. are mentioned. The aromatic hydrocarbon group may have two or more substituents, and the substituents in that case may be the same or different. When the aromatic hydrocarbon group has a substituent, it is preferable that the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is 6-18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

[0123] As an aromatic hydrocarbon group having 6 to 18 carbon atoms, specifically, a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, methoxyphenyl group, An ethoxyphenyl group, a butoxyphenyl group, and a t-butoxyphenyl group are mentioned. The position of the substituent in these aromatic hydrocarbon groups may be any of an ortho position, a meta position, and a para position. From the viewpoint of fluidity, an aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including a substituent is preferable, and an aryl group that is unsubstituted and having 6 to 10 carbon atoms or a substituent having 6 to 10 carbon atoms is more preferable. And a phenyl group, a p-tolyl group, and a p-methoxyphenyl group are more preferable.

[0124] 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} General Formula (I-1) means 2 of R ¹ to R ³ It means a case where two or three are bonded to form one divalent or trivalent hydrocarbon group as a whole. Examples of R ¹ to R ³ in this case include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure by bonding with a phosphorus atom, ethylenylene, propylenylene, butyl Alkenylene groups such as renylene groups, aralkylene groups such as methylenephenylene groups, and arylene groups such as phenylene, naphthylene, anthracenylene, and other substituents capable of forming a cyclic structure by bonding with a phosphorus atom are mentioned. have. These substituents may further be 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.

[0125] The "organic group having 1 to 18 carbon atoms" described as R ⁴ to R ⁷ in the general formula (I-1) is an aliphatic hydrocarbon group or an aromatic group having 1 to 18 carbon atoms and which does not need to be substituted even if substituted. It means containing a hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, an acyl group, a hydrocarbon oxycarbonyl group, and an acyloxy group.

[0126] Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group include those described above as examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R ¹ to R ³ .

[0127] 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, An oxy group having a structure in which an oxygen atom is bonded to the above-described aliphatic hydrocarbon group such as a cyclopentyloxy group, an allyloxy group, and a vinyloxy group, and these aliphatic hydrocarbon oxy groups are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, And those substituted with a halogen atom or the like.

[0128] As the aromatic hydrocarbon oxy group, an oxy group having an oxygen atom bonded to the above-described aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and a phenoxyphenoxy group, These aromatic hydrocarbon oxy groups further include those 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 aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, cyclohexylcarbonyl group, and allylcarbonyl group, aromatic hydrocarbon carbonyl groups such as phenylcarbonyl group and methylphenylcarbonyl group, and the like, these aliphatic hydrocarbon carbonyl groups or The aromatic hydrocarbon carbonyl group may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

[0130] Examples of the hydrocarbon oxycarbonyl group include an aliphatic hydrocarbon oxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an allyloxycarbonyl group, and a cyclohexyloxycarbonyl group, an aromatic hydrocarbon oxycarbonyl group such as a phenoxycarbonyl group and a methylphenoxycarbonyl group. And those wherein these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy 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.

[0131] Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, allylcarbonyloxy group, and cyclohexylcarbonyloxy group, and phenylcar. Aromatic hydrocarbon carbonyloxy groups such as carbonyloxy groups and methylphenylcarbonyloxy groups, and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are additionally alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms And the like substituted by the like.

[0132] 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 R ⁴ It means that -R ⁷ may combine to form one divalent to tetravalent organic group as a whole. Examples of R ⁴ to R ^{7 in} this case include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethylenylene, propylenylene, and butylene, and arals such as methylenephenylene. A substituent capable of forming a cyclic structure such as an arylene group such as a kilen group, phenylene, naphthylene, anthracenylene, or the like, and an oxy group or a dioxy group thereof. These substituents may further be 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 independently, is preferably 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. Among them, from the viewpoint of availability of raw materials, an aryl group substituted with at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an unsubstituted or alkyl group and an alkoxy group, or a chain or cyclic alkyl group desirable. Examples of the aryl group unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, and the like. Examples of the chain or cyclic alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, t-butyl group, octyl group, and cyclohexyl group. From the viewpoint of curability, it is preferable that all of R ⁴ to R ⁷ are hydrogen atoms, or a case where at least one of R ⁴ to R ⁷ is a hydroxyl group and all others are hydrogen atoms.

[0134] 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 all of R ⁴ to R ⁷ It is a hydrogen atom, or at least one is a hydroxyl group and all others are 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 fast curing properties, the specific curing accelerator is preferably a compound represented by the following general formula (I-2).

[0136]

[0137] 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 may be bonded to each other to form a cyclic structure. And 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 may be bonded to each other to form a cyclic structure.

[0138] Specific examples of R ¹ ~ R ⁶ in the formula (I-2) is the same as specific examples of R ¹ ~ R ⁶ in the formula (I-1), respectively, the preferred range is also the same .

[0139] Specific examples of a 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, 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 , An addition reaction product of 4-benzoquinone, an addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone, and the like.

Certain curing accelerators can be obtained, for example, as an adduct of a third phosphine compound and a quinone compound.

Specifically as a third phosphine compound, triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine Pine, 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-e) Methoxyphenyl)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.

As curing accelerators other than phosphonium compounds, specifically, 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) Cyclic amidine compounds such as diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; Derivatives of the cyclic amidine compounds; Phenol novolak salts of the cyclic amidine compounds or derivatives thereof; Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dime Quinone compounds such as oxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having intramolecular polarization obtained by adding a branched compound; Cyclic amidinium compounds such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; Tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; Derivatives of the tertiary amine compounds; Ammonium salt compounds, such as tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium phosphate, tetraethyl ammonium acetate, tetra-n-hexyl ammonium benzoate, and tetrapropyl ammonium hydroxide, etc. are mentioned.

[0143] When the curable resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator is preferably 30 mass% or more, more preferably 50 mass% or more, and 70 mass% or more of the total curing accelerator. It is more preferable.

When the curable resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass based on 100 parts by mass of the resin component. 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, there is a tendency for good curing in a short time. When 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 rate is not too fast, and a good molded article tends to be obtained.

[0145] (Inorganic filler)

The curable resin composition may contain an inorganic filler. In particular, when using the curable resin composition as a sealing material for a semiconductor package, it is preferable to include an inorganic filler.

[0146] 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, forsterite, steatite, spinel, mullite, Inorganic materials, such as titania, talc, clay, and mica, are mentioned. You may use an inorganic filler having a flame retardant effect. Examples of the inorganic filler having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate. Among them, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. Inorganic fillers may be used singly or in combination of two or more. Examples of the state of the inorganic filler include powder, beads in which the powder is spheroidized, and fibers.

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

[0148] The average particle diameter 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, the increase in viscosity of the resin composition for mold underfill tends to be more suppressed. When the volume average particle diameter is 10 μm or less, the filling property for 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.

[0149] 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, an organic solvent, nitric acid, aqua regia, or the like is used to extract the inorganic filler from the curable resin composition or the cured product, and sufficiently disperse with an ultrasonic disperser to prepare a dispersion. Using this dispersion, the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured by the laser diffraction scattering method particle size distribution measuring device. Alternatively, the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution obtained by burying the cured product in a transparent epoxy resin or the like and observing a cross section obtained by polishing with a scanning electron microscope. Further, it can also be measured by continuously observing the two-dimensional cross section of the cured product and performing three-dimensional structural analysis using an FIB device (focused ion beam SEM) or the like.

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 widely distributed.

[0151] [Various additives]

In addition to the above-described components, the curable resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress reliever as exemplified below. In addition to the additives illustrated below, the curable resin composition may contain various additives well known in the art as necessary.

[0152] (Coupling agent)

When the curable resin composition contains an inorganic filler, a coupling agent may be included in order to improve the adhesion between the resin component and the inorganic filler. Examples of the coupling agent include known coupling agents such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and other silane compounds, titanium compounds, aluminum chelate compounds, and aluminum/zirconium compounds. I can.

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, more preferably 0.1 parts by mass to 2.5 parts by mass based on 100 parts by mass of the inorganic filler. If 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 adhesion to 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.

[0154] (ion exchanger)

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

[0155] 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 is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferable that it is 0.1 mass part-30 mass parts with respect to 100 mass parts of resin components, and it is more preferable that it is 1 mass part-15 mass parts.

[0157] (release agent)

The curable resin composition may contain a releasing agent from the viewpoint of obtaining good releasability with a mold at the time of molding. The mold release agent is not particularly limited, and a conventionally known one can be used. Specifically, higher fatty acids such as carnauba wax, montanic acid, and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid ester, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, and the like can be mentioned. Releasing agents may be used singly or in combination of two or more.

When the curable resin composition contains a release agent, the amount is preferably 0.01 parts by mass to 15 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass based on 100 parts by mass of the resin component. When the amount of the releasing agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency for sufficient releasability to be obtained. If it is 15 parts by mass or less, there is a tendency for better adhesion to be obtained.

[0159] (flame retardant)

The curable resin composition may contain 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, and a metal hydroxide. Flame retardants may be used alone or in combination of two or more.

When the curable resin composition contains a flame retardant, the amount is not particularly limited as long as it is an amount sufficient to obtain a desired flame retardant effect. For example, it is preferable that it is 1 mass part-300 mass parts with respect to 100 mass parts of resin components, and it is more preferable that it is 2 mass parts-150 mass parts.

[0161] (Coloring agent)

The curable resin composition may further contain a colorant. As the colorant, known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, brisket, and Bengala may be mentioned. The content of the colorant can be appropriately selected depending on the purpose or the like. The coloring agent may be used individually by 1 type, or may be used in combination of 2 or more types.

[0162] (stress reliever)

The curable resin composition may contain a stress reliever such as silicone oil and silicone rubber particles. By including the stress reliever, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks. As the stress reliever, a generally used known stress reliever (flexible agent) can be mentioned. Specifically, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide and polybutadiene, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), Core-shells such as rubber particles such as acrylic rubber, urethane rubber, and silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer And rubber particles having a structure. Stress relievers may be used singly or in combination of two or more. Among them, silicone-based stress relievers are preferred. Examples of the silicone stress reliever include those having an epoxy group, those having an amino group, and those obtained by polyether modification thereof.

[0163] (Method for preparing a curable resin composition)

The preparation method of the curable resin composition is not particularly limited. As a general method, a method of sufficiently mixing a component of a predetermined blending amount by a mixer or the like, followed by melt-kneading by a mixing roll, an extruder, or the like, cooling, and grinding. More specifically, for example, a predetermined amount of the above-described ingredients is uniformly stirred and mixed, and kneaded with a kneader, roll, or extruder previously heated to 70°C to 140°C, cooling, and grinding How to do it.

It is preferable that the curable resin composition is a solid under normal temperature and pressure (eg, 25° C., under atmospheric pressure). The shape in the case where the curable resin composition is a solid is not particularly limited, and includes a powder type, a particle type, a tablet type, and the like. When the curable resin composition is a tablet type, it is preferable from the viewpoint of handling properties to make the size and mass suitable for the molding conditions of the package.

[0165] <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 sealing the element.

As electronic component devices, support members such as lead frames, wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, etc., and elements (active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils, etc.) The element part obtained by mounting (such as a passive element of)) is sealed with a curable resin composition.

More specifically, DIP having a structure in which an 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, etc., and then sealed by transfer molding or the like using a curable resin composition. (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), TQFP (Thin Quad) General resin-sealed ICs such as Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier by a bump is sealed with a curable resin composition; A COB (Chip On Board) module, a hybrid IC, a multi-chip module, etc. having a structure in which an element connected to the wiring formed on the supporting member by wire bonding, flip chip bonding, solder, or the like is sealed with a curable resin composition; BGA having a structure in which an element is mounted on the surface of a support member with terminals for wiring board connection formed on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, the element is sealed with a curable resin composition (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), and the like. Moreover, also in a printed wiring board, a curable resin composition can be used suitably.

As a method of sealing an electronic component device using the curable resin composition, a low pressure transfer molding method, an injection molding method, a compression molding method, and the like may be mentioned. Among these, the low-pressure transfer molding method is common.

Example

[0167] Hereinafter, the above embodiments will be specifically described with reference to Examples, but the scope of the above embodiments is not limited to these Examples.

[0168] [Preparation of curable resin composition]

The following materials were mixed in the composition (parts by mass) shown in Tables 1 to 3, and roll kneaded under conditions of a kneading temperature of 80°C and a kneading time of 15 minutes, thereby curing the curability of Examples 1 to 21 and Comparative Examples 1 to 10. A resin composition was prepared.

[0169] (epoxy resin)

Epoxy resin 1: Epoxy equivalent 196, melting point 106 ℃ biphenyl type epoxy resin (Mitsubishi Chemical Corporation, brand name "YX-4000H")

Epoxy resin 2: Styrene-modified phenol novolak type epoxy resin with an epoxy equivalent of 282 and a softening point of 59°C (NIPPON STEEL & SUMIKIN CHEMICAL CO. LTD., brand name "YDAN-1000-10C")

Epoxy resin 3: Epoxy equivalent 250, methoxynaphthalene-cresol formaldehyde co-condensation type epoxy resin with a softening point of 58°C (DIC Corporation, brand name "HP-5000")

Epoxy resin 4: An aralkyl type epoxy resin containing a biphenylene skeleton with an epoxy equivalent of 282 and a softening point of 56°C (Nippon Kayaku Co., Ltd., brand name "NC-3000")

[0170] (hardener)

Curing agent 1: phenol aralkyl resin with a hydroxyl equivalent weight of 176 and a softening point of 70℃ (MEIWA PLASTIC INDUSTRIES, LTD., brand name "MEH-7800")

Hardener 2: Biphenyl skeletal phenol aralkyl resin with a hydroxyl equivalent weight of 199 and a softening point of 89°C (MEIWA PLASTIC INDUSTRIES, LTD., brand name "MEH-7851")

[0171] (triazine compound)

Triazine compound 1; 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(octyloxy)-phenol (Cytec company, brand name "UV-1164" )

Triazine compound 2; 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-[(2-ethylphenyl)oxy]-2-hydroxy Propoxy]phenol (manufactured by BASF, brand name "Tinuvin405")

Triazine compound 3; 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (ADEKA CORPORATION, brand name ``Adecastav LA-F70'')

Triazine compound 4; 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol (BASF company, brand name "Tinuvin1577")

Triazine compound 5; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (ADEKA CORPORATION, brand name "adecastab LA-46」)

Triazine compound 6; 2-[4-[4,6-bis[(1,1'-biphenyl)-4-yl]-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]isooctyl Propanoate (BASF, brand name "Tinuvin479")

Triazine compound 7; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

Triazine compound 8; 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

Triazine compound 9; 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

Triazine compound 10; 2,4,6-triphenyl-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

Triazine compound A; Melamine (Tokyo Chemical Industry Co., Ltd., reagent)

Triazine compound B; Benzoguanamine (Tokyo Chemical Industry Co., Ltd., reagent)

[0172] (hardening accelerator)

Curing accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone

(Inorganic filling)

Spherical fused silica (average particle diameter 17.5μm, specific surface area 3.8m ² /g)

(Coupling agent)

Epoxysilane (γ-glycidoxypropyltrimethoxysilane)

(coloring agent)

Carbon black (Mitsubishi Chemical Corporation, brand name "MA-100")

(Release agent)

Carnauba wax (CERARICA NODA Co., Ltd.)

[0173] [Table 1]

[0174] [Table 2]

[0175] [Table 3]

[0176] [Evaluation of Epoxy Resin Molding Material for Sealing]

The properties of the epoxy resin molding materials for sealing produced in Examples 1 to 21 and Comparative Examples 1 to 10 were evaluated by the following characteristic tests. The evaluation results are shown in Tables 4-6 below. In addition, the molding of the sealing epoxy resin molding material 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. Further, if necessary, post-curing was performed at 175°C for 5 hours.

[0177] (1) Spiral flow

Using a mold for measuring spiral flow according to EMMI-1-66, an epoxy molding material for sealing was molded under the above conditions, and a flow distance (cm) was calculated.

[0178] (2) Hardness at thermal time

The epoxy resin molding material for sealing is molded into a disc having a diameter of 50 mm x a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D-type hardness tester (manufactured by Ueshima Seisakusho Co., Ltd., HD-1120 (Type D)) It was measured using.

[0179] (3) 260℃ shear adhesion

Under the above conditions, the epoxy resin molding material for sealing was molded into a size of a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm on a silver-plated copper plate, and post-cured under the above conditions. Thereafter, using a bond tester (Nordson Advanced Technology (Japan) K.K., series 4000), while maintaining the temperature of the copper plate at 260°C, shear adhesion (MPa) was obtained at a shear rate of 50 μm/s.

[0180] (4) Water absorption

The original plate molded in (2) was post-cured under the above conditions. Thereafter, the obtained original plate was allowed to stand for 168 hours under conditions of 85°C and 60% RH (relative humidity), and the mass change before and after standing was measured. The water absorption was calculated from the measurement result by the following formula.

Absorption rate (% by mass) = (mass of the disk after standing-mass of the disk before standing) / mass of the disk before standing × 100

[0181] (5) Reflowability

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

[0182] [Table 4]

[0183] [Table 5]

[0184] [Table 6]

[0185] As shown in Tables 4 to 6, Examples 1 to 21 containing the triazine compounds 1 to 10 corresponding to the specific triazine compound compared to Comparative Examples 1 to 8 not containing the triazine compound, The adhesion to metal (silver) is improved, and the reflow property is also improved.

Comparative Examples 9 and 10 containing triazine compounds A and B that do not correspond to a specific triazine compound are compared with Comparative Examples 1 to 8 not containing a triazine compound, and adhesion to metal (silver) and anti-flow properties. Couldn't see any improvement.

Claims (13)

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

[In General Formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon group.] The method of claim 1,
A curable resin composition in which the compound represented by the general formula (1) contains a compound represented by the following general formula (2).

[In the general formula (2), R ⁴ to R ⁶ are each independently an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an aromatic hydrocarbon amino group, It is a monovalent group selected from the group consisting of an aliphatic hydrocarbon amino group, a diaromatic hydrocarbon amino group, a dialiphatic hydrocarbon amino group, and an aromatic hydrocarbon aliphatic hydrocarbon amino group. Each n is independently an integer of 0-5.] The method of claim 2,
At least one of the R ⁴ to R ⁶ is a hydroxyl group, the curable resin composition. The method according to any one of claims 1 to 3,
Curable resin composition further comprising an inorganic filler. The method according to any one of claims 1 to 4,
Curable resin composition wherein the curable resin comprises an epoxy resin. The method of claim 5,
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 novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, and triphenylmethane-type epoxy resin. Curable resin composition comprising at least one selected from the group consisting of a copolymer-type epoxy resin, and an aralkyl-type epoxy resin. The method according to any one of claims 1 to 6,
Curable resin composition further comprising a curing agent. The method of claim 7,
The curing agent is selected from the group consisting of aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, benzaldehyde type phenol resin and aralkyl type phenol resin, and novolak type phenol resin. Curable resin composition containing at least 1 type. The method according to any one of claims 1 to 8,
Curable resin composition further comprising a curing accelerator. The method of claim 9,
The curing accelerator is a curable resin composition containing a phosphonium compound. The method of claim 9 or 10,
The curable resin composition containing a compound represented by the following general formula (I-1) as the 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, Also, 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 may be bonded to each other to form a cyclic structure.] The method of claim 11,
A curable resin composition in which the compound represented by the general formula (I-1) contains 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 may be bonded to each other to form a cyclic structure, and 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 may be bonded to each other to form a cyclic structure.] An electronic component device comprising an element and a cured product of the curable resin composition according to any one of claims 1 to 12 for sealing the element.