TW202000767A - Curable resin composition and electronic device - Google Patents

Abstract

A curable resin composition, comprising a curable resin and a compound represented by the following Formula (1):

wherein, in Formula (1), each of R¹ to R³ independently represents a monovalent hydrocarbon group.

Description

Curable resin composition and electronic parts device

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

With the recent miniaturization, weight reduction, and high performance of electronic devices, the density of installations has been continuously increased. As a result, the mainstream of electronic component devices has changed from existing pin-inserted packages to surface mount packages such as integrated circuits (ICs) and large scale integrated circuits (LSIs).

The installation method of the surface mount package is different from the existing pin insertion type package. That is, when the pins are mounted on the wiring board, the conventional pin insertion type package is to solder the pins from the back of the wiring board after inserting the pins into the wiring board, so the package is not directly exposed to high temperature. However, in the surface mount type package, the entire electronic component device is processed with a solder bath, a reflow device, etc., so the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture rapidly expands due to moisture absorption during soldering, and the generated vapor pressure acts as a peeling stress, which causes peeling between the interposer such as an element, a lead frame, and the sealing material. In some cases, it may cause cracks in the package or poor electrical characteristics. Therefore, it is desired to develop a sealing material that is excellent in adhesiveness with respect to an insert and further has excellent solder heat resistance (reflow resistance).

In order to meet the above-mentioned requirements, as a modified material of the inorganic filler contained in the sealing material, the use of a silane coupling agent has been studied. Specifically, the use of epoxy group-containing silane coupling agents or amine group-containing silane coupling agents (for example, see Patent Document 1), sulfur atom-containing silane coupling agents (for example, see Patent Document 2), etc. . [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-147939 [Patent Document 2] Japanese Patent Laid-Open No. 2000-103940

[Problems to be solved by the invention]

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

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

The means for solving the above-mentioned problems include the following embodiments. <1> A curable resin composition comprising: a curable resin; and a compound represented by the following general formula (1).

通式（1）中，R¹ ～R³ 分別獨立地表示一價烴基。[Chemical 1]

In the 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).

通式（2）中，R⁴ ～R⁶ 分別獨立地為選自由芳香族烴基、脂肪族烴基、脂肪族烴氧基、芳香族烴氧基、羥基、羧基、鹵素原子、胺基、芳香族烴胺基、脂肪族烴胺基、二芳香族烴胺基、二脂肪族烴胺基及芳香族烴脂肪族烴胺基所組成的群組中的一價基。n分別獨立地為0～5的整數。[Chem 2]

In the general formula (2), R ⁴ to R ⁶ are each independently selected from the group consisting of aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, and aromatic groups A monovalent group in the group consisting of a hydrocarbon amine group, an aliphatic hydrocarbon amine group, a diaromatic hydrocarbon amine group, a dialiphatic hydrocarbon amine group, and an aromatic hydrocarbon aliphatic hydrocarbon amine group. 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>, which further contains 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> The curable resin composition according to <5>, wherein the epoxy resin contains a resin selected from the group consisting of biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, and It consists of sulfur atom epoxy resin, novolac epoxy resin, dicyclopentadiene epoxy resin, triphenylmethane epoxy resin, copolymer epoxy resin and aralkyl epoxy resin At least one of the group. <7> The curable resin composition according to any one of <1> to <6>, which further contains a curing agent. <8> The curable resin composition according to <7>, wherein the curing agent comprises a aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, benzaldehyde At least one of the group consisting of a copolymerized phenol resin of a type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. <9> The curable resin composition according to any one of <1> to <8>, which further contains a curing accelerator. <10> The curable resin composition according to <9>, wherein the curing accelerator contains a phosphonium compound. <11> The curable resin composition according to <9> or <10>, wherein the curing accelerator contains a compound represented by the following general formula (I-1).

式（I-1）中，R¹ ～R³ 分別獨立地為碳數1～18的烴基，R¹ ～R³ 中的兩個以上可相互鍵結而形成環狀結構；R⁴ ～R⁷ 分別獨立地為氫原子、羥基或碳數1～18的有機基，R⁴ ～R⁷ 中的兩個以上可相互鍵結而形成環狀結構。[Chemical 3]

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 ring structure; R ⁴ to R ⁷ Each is 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 ring 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).

式（I-2）中，R¹ ～R³ 分別獨立地為碳數1～18的烴基，R¹ ～R³ 中的兩個以上可相互鍵結而形成環狀結構；R⁴ ～R⁶ 分別獨立地為氫原子或碳數1～18的有機基，R⁴ ～R⁶ 中的兩個以上可相互鍵結而形成環狀結構。[Chemical 4]

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 ring structure; R ⁴ to R ⁶ Each is 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 ring structure.

<13> An electronic component device comprising: an element; and a cured product of the curable resin composition according to any one of <1> to <12> that seals the element. [Effect of invention]

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

Hereinafter, a mode for implementing the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps, etc.) are not required unless specifically stated otherwise. The same is true for numerical values and ranges, and does not limit the present invention.

In the present disclosure, the term "step" includes a step that is independent of other steps, even if it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved. In the present disclosure, numerical values described before and after including "-" in the numerical range indicated by "-" are used as the minimum value and the maximum value, respectively. In the numerical range described in stages in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In addition, in the described numerical range, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. In the present disclosure, regarding the content rate or content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it refers to the presence in the composition The total content rate or content of multiple substances. In the present disclosure, when the particle size of each component in the composition includes a plurality of particles corresponding to each component in the composition, unless otherwise specified, it refers to the mixture of the plurality of particles present in the composition value.

<Curable resin composition> The curable resin composition as an embodiment of the present disclosure includes: a curable resin; and a compound represented by the following general formula (1) (hereinafter, also referred to as a specific triazine compound). According to studies by the present inventors and others, the curable resin composition containing a specific triazine compound has excellent adhesion to metals (especially precious metals such as gold and silver) in a cured state. The reason is not clear, but it is speculated that the specific triazine compound in the hardened substance forms a coordination bond with the metal.

The curable resin composition containing a specific triazine compound is excellent in the adhesion to metal in the cured state. Therefore, when used as a sealing material for a package including a lead frame whose material is at least the surface of a metal, the lead frame and Peeling between sealing materials. Therefore, the reflow resistance is excellent.

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

[Chem 5]

In the 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, aromatic hydrocarbon groups and aliphatic hydrocarbon groups may be mentioned.

Examples of the aromatic hydrocarbon group include phenyl and naphthyl. Examples of the aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, and alicyclic hydrocarbon groups having 3 to 18 carbon atoms.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and third butyl. Alkyl, allyl, vinyl, etc. such as pentyl, hexyl, octyl, decyl, dodecyl, etc.

Specific examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl and other cycloalkyl groups, adamantyl groups, and norbornyl groups. , Dicyclopentyl and so on.

The monovalent hydrocarbon group represented by R ¹ to R ³ may have a substituent. Examples of the substituent include aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic hydrocarbon amine groups, aliphatic hydrocarbon amine groups, and dihydrocarbyl groups. Aromatic hydrocarbon amine groups, dialiphatic hydrocarbon amine groups, aromatic hydrocarbon aliphatic hydrocarbon amine groups, etc.

Examples of the aromatic hydrocarbon group include phenyl and naphthyl. Examples of the aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, and alicyclic hydrocarbon groups having 3 to 18 carbon atoms. Examples of the aromatic hydrocarbon oxy group include a group having an oxygen atom bonded to an aromatic hydrocarbon group such as phenyl group and naphthyl group. Examples of the aliphatic hydrocarbon oxy group include a group having an oxygen atom 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 carbon number of the monovalent hydrocarbon group represented by R ¹ to R ³ is not particularly limited. For example, it is preferable that each of them independently has 1 to 30 carbon atoms. When the monovalent hydrocarbon group represented by R ¹ to R ³ has a substituent, the carbon atoms contained in the substituent are also included in "the number of carbon atoms of the monovalent carbon atom".

In one embodiment, at least one of the monovalent hydrocarbon groups represented by R ¹ to R ³ is a phenyl group, and in one 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).

[化6]

In the general formula (2), R ⁴ to R ⁶ are each independently selected from the group consisting of aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, and aromatic groups A monovalent group in the group consisting of a hydrocarbon amine group, an aliphatic hydrocarbon amine group, a diaromatic hydrocarbon amine group, a dialiphatic hydrocarbon amine group, and an aromatic hydrocarbon aliphatic hydrocarbon amine group. n is independently an integer of 0-5.

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

In one embodiment, the specific triazine compound is one or two of R ¹ to R ³ in the general formula (1) being 2,4-dimethylphenyl. In one embodiment, two of R ¹ to R ³ are 2,4-dimethylphenyl and one is 2-hydroxy-4-n-octyloxyphenyl. Specific examples of the specific triazine compound include compounds having a structure represented by the following formula.

[化7]

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 the adhesion to gold and silver, for example, the total of the curable resin contained in the curable resin composition and the hardener used as necessary (hereinafter, also referred to as "resin component" ") 100 parts by mass, preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and still more preferably 3.0 parts by mass or more. From the viewpoint of curability, for example, with respect to 100 parts by mass of the resin component, 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.

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

The functional group that generates the reaction of the curable resin is not particularly limited, and examples thereof include cyclic ether groups such as epoxy groups and oxetanyl groups, hydroxyl groups, carboxyl groups, amine groups, acrylonitrile groups, isocyanate groups, and maleimide groups. Amino, alkenyl, etc. From the viewpoint of balancing the characteristics of the 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 epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples include phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and α-naphthol, β-naphthol, diphenol At least one phenolic compound in the group consisting of hydroxynaphthalene and other naphthol compounds is condensed or co-condensed with formaldehyde, acetaldehyde, propionaldehyde and other aliphatic aldehyde compounds under an acid catalyst to obtain a novolak resin and the novolak resin Novolak-type epoxy resins obtained by epoxidation of resins (phenol novolak-type epoxy resins, o-cresol novolak-type epoxy resins, etc.); the aromatic compounds such as benzaldehyde and salicylaldehyde A triphenylmethane type epoxy resin obtained by condensing or co-condensing an aldehyde compound under an acid catalyst to obtain a triphenylmethane type phenol resin and epoxidizing the triphenylmethane type phenol resin; making the phenol compound Co-condensation of naphthol compound and aldehyde compound under acid catalyst to obtain novolak resin and epoxidation of the novolak resin; copolymerized epoxy resin obtained as bisphenol A, bisphenol F, etc. Diphenylmethane epoxy resin of glyceryl ether; biphenyl epoxy resin as diglycidyl ether of alkyl substituted or unsubstituted biphenol; diglycidyl as stilbene phenol compound Distyrene-type epoxy resin of ether; sulfur atom-containing epoxy resin as diglycidyl ether of bisphenol S; ring of glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, etc. Oxygen resin; glycidyl ester epoxy resin as glycidyl ester of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; aniline, diaminodiphenylmethane, iso A glycidylamine-type epoxy resin obtained by replacing active hydrogen bonded to a nitrogen atom such as cyanuric acid with a glycidyl group; a dicyclopentadiene and phenol compound co-condensation resin is obtained by epoxidation. Cyclopentadiene type epoxy resin; diepoxy vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane obtained by epoxidation of olefin bond in the molecule Carboxylic acid esters, 2-(3,4-epoxy)cyclohexyl-5,5-spiro (3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; as Para-xylene modified epoxy resin of glycidyl ether of para-xylene modified phenol resin; meta-xylene modified epoxy resin of glycidyl ether of meta-xylene modified phenol resin; modified terpene phenol resin Terpene-modified epoxy resin of glycidyl ether; dicyclopentadiene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; as a shrinkage of cyclopentadiene-modified phenol resin Glycerol-cyclopentadiene-modified epoxy resin; Polycyclic aromatic-ring-modified epoxy resin as glycidyl ether of polycyclic aromatic ring-modified phenol resin; Naphthalene as glycidyl ether of phenol resin containing naphthalene ring Type epoxy resin; halogenated phenol novolak type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic obtained by oxidizing olefin bond with peracid such as peracetic acid Epoxy resin; obtained by epoxidizing aralkyl type phenol resins such as phenol aralkyl resin, naphthol aralkyl resin Aralkyl type epoxy resin etc. Furthermore, epoxy resin of silicone resin, epoxy resin of acrylic resin, etc. can also be mentioned. These epoxy resins may be used alone or in combination of two or more.

Among the epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, it is preferably selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, and diphenylmethane type epoxy resins. , Epoxy resin containing sulfur atom, novolac epoxy resin, dicyclopentadiene epoxy resin, triphenylmethane epoxy resin, copolymer epoxy resin and aralkyl epoxy resin The epoxy resin in the group (referred to as "specific epoxy resin"). The specific epoxy resin may be used alone or in combination of two or more.

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

From the viewpoint of fluidity, the specific epoxy resin is more preferably a biphenyl-type epoxy resin, a styrene-type epoxy resin, a diphenylmethane-type epoxy resin, or a sulfur atom-containing epoxy resin. From the viewpoint of properties, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin or aralkyl type epoxy resin is preferable. The following shows specific examples of preferred epoxy resins.

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

[Chem 8]

In formula (II), R ⁸ represents a hydrogen atom, a C 1-12 alkyl group or a C 4-18 aromatic group, and each may be the same or different. n is the 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, it is preferably an epoxy resin represented by the following general formula (III). In the epoxy resin represented by the following general formula (III), when the oxygen atom substitution position in R ⁹ is set to the 4 position and the 4'position, the 3, 3', 5, 5'positions are methyl groups and except this In addition to the case where R ⁹ is a hydrogen atom and R ¹⁰ is a hydrogen atom, and 3 of the 3, 3', 5, 5'positions of R ⁹ are methyl and 1 is a third butyl and other When R ⁹ is a hydrogen atom and R ¹⁰ is a hydrogen atom, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), etc., which are mixed products, are available as commercially available products.

[化9]

In formula (III), R ⁹ and R ¹⁰ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is the 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, it is preferably an epoxy resin represented by the following general formula (IV). In the epoxy resin represented by the following general formula (IV), R ¹¹ is a hydrogen atom, and the oxygen atom in R ¹² is substituted with 3, 3', 5, 5'when the positions of the 4 position and 4'position are substituted YSLV-80XY (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name) etc., which is a methyl group and other than R ¹² is a hydrogen atom, can be obtained as a commercially available product.

[化10]

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

The sulfur atom-containing epoxy resin is not particularly limited as long as it contains sulfur atoms. For example, the epoxy resin represented by the following general formula (V) can be mentioned. In the epoxy resin represented by the following general formula (V), when the oxygen atom in R ¹³ is substituted at the 4 and 4'positions, the 3,3' position is the third butyl, 6,6' position YSLV-120TE (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name) which is a methyl group and other R ¹³ is a hydrogen atom can be obtained as a commercially available product.

[Chem 11]

In formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. n is the 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 novolak-type phenol resin. For example, epoxy resins obtained by epoxidation of novolak-type phenol resins such as phenol novolak resin, cresol novolak resin, naphthol novolak resin, and the like using glycidyl etherification are preferred. The epoxy resin represented by formula (VI). In the epoxy resin represented by the following general formula (VI), R ^{14 is} all hydrogen atoms, R ¹⁵ is methyl group, ESN-190 and ESCN-195 (Sumitomo Chemical Co., Ltd., trade name) with i=1; R ¹⁴ are all hydrogen atoms, i = N-770 0 a, N-775 (DIC (DIC) Co., Ltd., trade name); with R ¹⁴ are all hydrogen atoms, i = 0 and the portion of i = 1, R ¹⁵ is -CH(CH ₃ )-Ph part of styrene modified phenol novolak type epoxy resin, that is, YDAN-1000-10C (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name); as having R ^{14 are} all hydrogen atoms, i=1, R ¹⁵ is a methyl portion and i=2, one of R ¹⁵ is a methyl group, and one is a benzyl portion of a benzyl modified cresol novolac epoxy resin , That is, HP-5600 (DIC) Co., Ltd., trade name, etc. can be obtained as a commercially available product.

[化12]

In formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i independently represents the integer of 0-3. n is the 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 epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, the epoxy resin represented by the following general formula (VII) is preferable. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC) Co., Ltd. (trade name) with i=0 can be obtained as a commercially available product.

[Chem 13]

In formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i independently represents the integer of 0-3. n is the 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 using a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by glycidyl etherification of triphenylmethane-type phenol resin such as a novolac-type phenol resin having a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferred, and the following is more preferred The epoxy resin represented by the general formula (VIII). Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Co., Ltd., trade name), EPPN-502H (Nippon Chemical Co., Ltd., trade name), etc. where i is 0 and k is 0 Available as a commercial product.

[化14]

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

The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound and an aldehyde compound, as long as the compound has a naphthol skeleton compound and a phenol skeleton compound as raw materials , There is no particular limitation. For example, an epoxy resin obtained by subjecting a novolac type phenol resin having a compound having a naphthol skeleton and a compound having a phenol skeleton to glycidyl etherification is preferable, and a ring represented by the following general formula (IX) is more preferable. Oxygen resin. Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name) etc. where R ²¹ is a methyl group, i is 1, j is 0, and k is 0 can be used as Obtained from commercially available products.

[化15]

In formula (IX), R ¹⁹ to R ²¹ represent a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different. i independently represents an integer of 0 to 3, j independently represents an integer of 0 to 2, and k independently represents an integer of 0 to 4. l and m are the average values, which are the numbers from 0 to 10, (l+m) means the numbers from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either of the following formula (IX-1) or formula (IX-2). In formula (IX-1) and formula ^{(IX-2), R 19} ~ R 21 is i, in the definition of formula (IX) j and k is R ¹⁹ ~ R ²¹ is i, j and k are defined the same. n is 1 (when bonding through methylene group) or 0 (when bonding without methylene group).

[Chem 16]

Examples of the epoxy resin represented by the general formula (IX) include: random copolymers that randomly include one structural unit and m structural units, and those that alternately include one structural unit and m structural units Alternating copolymers, copolymers that regularly contain one structural unit and m structural units, block copolymers that contain one structural unit and m structural units in block form, and the like. Any one of these may be used alone, or two or more kinds may be used in combination.

As the copolymerization type epoxy resin, methoxynaphthalene·cresol formaldehyde co-condensation type epoxy resin containing the following two structural units in random, alternating, or block order is also preferable, that is, the following The general expression of Epiclon (EPICLON) HP-5000 (DIC), trade name). In the following general formulas, n and m are the average values, respectively, a number of 0-10, (n+m) represents the number of 0-10, preferably n and m are the average values, respectively, the number of 1-9 , (N+m) represents a number from 2 to 10.

[化17]

The aralkyl type epoxy resin should be at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol. The epoxy resin as the raw material of the phenol resin synthesized from toluene, bis(methoxymethyl)biphenyl or these derivatives is not particularly limited. For example, it is preferable that at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol is combined with dimethoxy-p-xylene and bis(methoxy) The epoxy resin obtained by glycidyl etherification of the phenol resin synthesized by the base methyl) biphenyl or these derivatives is more preferably an epoxy resin represented by the following general formula (X) and general formula (XI) Resin.

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

[Chemical 18]

In formula (X) and formula (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and 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 may be the same or different. i is independently an integer of 0 to 3, j is independently an integer of 0 to 2, k is independently an integer of 0 to 4, and l is independently an integer of 0 to 6, respectively. n is an average value, and is independently a number from 0 to 10.

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

In the general formula (II) to the general formula (XI), n is an average value, and it is preferably independently in the range of 0 to 10. If n is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the curable resin composition during melt molding will be reduced, and the occurrence of poor filling and deformation of the bonding wire (metal wire connecting the element and the lead) will be suppressed Propensity. n is more preferably set in the range of 0 to 4.

The functional group equivalent of the curable resin (epoxy equivalent in the case of epoxy resin) is not particularly limited. From the viewpoint of the balance of various characteristics such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of the curable resin is preferably 100 g/eq to 1000 g/eq, 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 reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of workability at the time of preparing the curable resin composition, more preferably 50°C to 130°C.

From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the content 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 %.

(hardener) The curable resin composition may contain a curing agent. The type of curing agent is not particularly limited, and can be selected according to the type of curable resin, desired characteristics of the curable resin composition, and the like. Examples of the curing agent when the curable resin is an epoxy resin include phenolic curing agents, amine curing agents, anhydride curing agents, polythiol curing agents, polyamine amide curing agents, isocyanate curing agents, and block isocyanate curing agents. Agent. From the viewpoint of coexistence of curability and pot life, it is preferably at least one selected from the group consisting of phenolic hardeners, amine hardeners, and acid anhydride hardeners, and from the viewpoint of electrical reliability, more preferably Phenol hardener.

Examples of the phenol hardener include phenol resins and polyphenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol, etc.; selected from phenol, cresol, xylenol , Resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenol compounds and α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds Novolac-type phenol resin obtained by condensation or co-condensation of at least one phenolic compound in the group with formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and other aldehyde compounds under an acid catalyst; Phenolic aralkyl resins, naphthol aralkyl resins and other aralkyl-type phenol resins synthesized by synthetic compounds and dimethoxy-p-xylene, bis(methoxymethyl) biphenyl, etc.; p-xylene and/ Or m-xylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene type phenol resin synthesized by copolymerization of the phenolic compound and dicyclopentadiene and Dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; the phenolic compound and benzaldehyde, salicylaldehyde and other aromatic A triphenylmethane type phenol resin obtained by condensation or co-condensation of an aldehyde compound under an acid catalyst; a phenol resin obtained by copolymerizing two or more of these. These phenol hardeners may be used alone or in combination of two or more.

Among the phenol hardeners, from the viewpoint of reflow resistance, it is preferably selected from the group consisting of aralkyl type phenol resins, dicyclopentadiene type phenol resins, triphenylmethane type phenol resins, and benzaldehyde type phenol resins. At least one of the group consisting of a copolymerized phenol resin of an aralkyl type phenol resin and a novolak type phenol resin (these are called "specific phenol hardeners"). The specific phenol hardener may be used alone or in combination of two or more.

When the hardener contains a specific phenol hardener, the content of the specific phenol hardener is preferably 30% by mass or more of the entire hardener, more preferably 50% by mass from the viewpoint of fully exhibiting these properties. the above

Examples of the aralkyl type phenol resins include phenol aralkyl resins and naphthol aralkyl resins synthesized from phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, and the like. . The aralkyl type phenol resin can be further copolymerized with other phenol resins. Examples of the copolymerized aralkyl type phenol resin include: a copolymerized type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a copolymerized type of a salicylaldehyde type phenol resin and an aralkyl type phenol resin. Phenolic resin, novolak type phenol resin and aralkyl type phenol resin copolymerization type phenol resin, etc.

The aralkyl type phenol resin may be derived from at least one selected from the group consisting of phenol compounds and naphthol compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or these The phenol resin synthesized from the substance is not particularly limited. For example, the phenol resin represented by the following general formula (XII) to general formula (XIV) is preferable.

[Chem 19]

In formula (XII) to formula (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each 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 may be the same or different from each other. R ²⁶ and R ²⁷ represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. i is independently an integer of 0 to 3, j is independently an integer of 0 to 2, k is independently an integer of 0 to 4, and p is independently an integer of 0 to 4. n is an average value, and is independently a number from 0 to 10.

Among the phenol resins represented by the general formula (XII), MEH-7851 (Meiwa Chemical Co., Ltd., trade name), etc. where i is 0 and R ²³ are all hydrogen atoms are available as commercially available products.

Among the phenol resins represented by the general formula (XIII), XL-225, XLC (Mitsui Chemical Co., Ltd., trade name) and MEH-7800 (Minghe Chemical Industry Co., Ltd., trade name) where i is 0 and k is 0 ) Etc. can be obtained as a commercially available product.

In the phenol resin represented by the general formula (XIV), j is 0, k is 0 and p is 0 of SN-170 (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name), j is 0, and k is 1 SN-395 (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name) where R ²⁷ is a hydroxyl group and p is 0 is available as a commercially available product.

The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a dicyclopentadiene skeleton as a raw material. For example, the phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (new Nippon Petrochemical Co., Ltd., trade name) and the like where i is 0 can be obtained as a commercially available product.

[化20]

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

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

Among the phenol resins represented by the following general formula (XVI), MEH-7500 (Meiwa Chemical Co., Ltd., trade name), etc. where i is 0 and k is 0 are available as commercially available products.

[化21]

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

The copolymerization type phenol resin of the benzaldehyde type phenol resin and the aralkyl type phenol resin as long as it is a copolymer type phenol resin obtained by using a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenol resin, and No particular limitation. For example, the 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 Co., Ltd., trade name), etc. where i is 0, k is 0, and q is 0 are commercially available Products.

[化22]

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

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

In the phenol resin represented by the following general formula (XVIII), Tamanol 758, 759 (Arakawa Chemical Industry Co., Ltd., trade name), HP-850N (i is 0, R ³⁵ are hydrogen atoms) Hitachi Chemical Co., Ltd., trade name) etc. are available as commercial products.

[化23]

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

The "may be all the same or different" described in R ²² to R ³⁶ in the general formula (XII) to the general formula (XVIII), for example, means that the i R ²² in the formula (XII) may all be the same or Different from each other. The other R ²³ to R ³⁶ mean that the respective numbers included in the formula may be the same or different from each other. In addition, R ²² to R ³⁶ may be the same or different. For example, R ²² and R ²³ may be the same or different, and R ³⁰ and R ³¹ may be the same or different.

In the general formula (XII) to the general formula (XVIII), n is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the curable resin composition during melt molding will also be low, and no poor filling occurs or it is difficult to produce bonding wires (metal wires connecting the element and the lead) Deformed. The average n in 1 molecule is preferably set in the range of 0 to 4.

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

The softening point or melting point of the hardener is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of operability at the time of manufacturing the curable resin composition, more preferably 50°C to 130°C.

The equivalent ratio of the curable resin to 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 the respective unreacted components, it is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is more preferably set to a range of 0.8 to 1.2.

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

From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-toluene)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl·alkoxy Phenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine, tri(trialkyl Tertiary phosphine such as alkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; maleic anhydride, 1,4- Benzoquinone, 2,5-toluone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl Addition of quinone compounds such as -1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds with a π bond such as diazophenylmethane And a compound with intramolecular polarization formed; to make the tertiary phosphine or the phosphine compound with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2 -Chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethyl Phenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6 -Compounds with intramolecular polarization obtained after the reaction of halogenated phenol compounds such as bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and the like after dehydrohalogenation; tetra-substituted phosphonium such as tetraphenylphosphonium, Tetra-p-toluene borate, etc. Tetra-substituted phosphonium and tetra-substituted borate without phenyl group bonded to boron atom; salts of tetra-substituted phosphonium and anions after deprotonation from phenol compounds, tetra-substituted phosphonium and self-carboxylic acid compounds Salts of anions after leaving protons.

Among the phosphonium compounds, compounds represented by the following general formula (I-1) (hereinafter, also referred to as specific hardening accelerators) are preferred.

[化24]

In formula (I-1), R ¹ to R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, two or more of R ¹ to R ³ may be bonded to each other to form a ring structure, and R ⁴ to R ⁷ Each is 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 ring structure.

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.

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 even more preferably 4 to 6.

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, a linear or branched aliphatic hydrocarbon group is preferred.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and third butyl. Alkyl, allyl, vinyl, etc. such as pentyl, hexyl, octyl, decyl, dodecyl, etc. The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkoxy groups such as methoxy, ethoxy, butoxy, and third butoxy groups, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amine groups, and halogen atoms. The linear or branched aliphatic hydrocarbon group may have two or more substituents, and the substituents at this time may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbons contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18. From the viewpoint of curability, unsubstituted alkyl groups are preferred, unsubstituted alkyl groups having 1 to 8 carbon atoms are more preferred, and n-butyl, isobutyl, n-pentyl, and n-hexyl are more preferred Base and n-octyl.

Specific examples of the alicyclic hydrocarbon having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, cyclopentenyl groups, and cycloalkenyl groups such as cyclohexenyl. The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, butyl, and third butyl groups, alkoxy groups such as methoxy, ethoxy, butoxy, and third butoxy groups, phenyl, and naphthalene. Aryl groups, hydroxyl groups, amine groups, halogen atoms, etc. The alicyclic hydrocarbon group may have two or more substituents, and the substituents at this time may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbons contained in the alicyclic hydrocarbon group and the substituent is preferably 3 to 18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of curability, unsubstituted cycloalkyl groups are preferred, unsubstituted cycloalkyl groups having 4 to 10 carbon atoms are more preferred, and cyclohexyl, cyclopentyl, and cycloheptyl groups are more preferred.

The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, more preferably 6 to 10. The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, butyl, and third butyl groups, alkoxy groups such as methoxy, ethoxy, butoxy, and third butoxy groups, phenyl, and naphthalene. Aryl groups, hydroxyl groups, amine groups, halogen atoms, etc. The aromatic hydrocarbon group may have two or more substituents, and the substituents at this time may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6 to 18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, and butylphenyl. Third butylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, third butoxyphenyl. The position of the substituent in these aromatic hydrocarbon groups may be any of ortho, meta, and para. From the viewpoint of fluidity, it is preferably an unsubstituted aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including a substituent, and more preferably an unsubstituted aryl group having 6 to 10 carbon atoms or The C6-C10 aryl group containing a substituent is further preferably phenyl, p-tolyl, and p-methoxyphenyl.

The term general formula (I-1) R ¹ ~ R ³ is described in "two or more R may be bonded to each other in the ¹ ~ R ³ form a cyclic structure" refers to the R ¹ ~ R ³ 2 th Or 3 bonds, the whole becomes a divalent or trivalent hydrocarbon group. Examples of R ¹ to R ³ at this time include ethylidene, propylidene, butylidene, pentylidene, and hexylidene groups that can form a cyclic structure by bonding to a phosphorus atom. Alkenyl such as ethynyl, propynyl, butynyl, aralkylene such as methylene phenylene, phenylene, naphthyl, anthracenyl, etc. The substituents that are bonded to form a ring structure. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, hydroxyl groups, halogen atoms, and the like.

The "organic group having 1 to 18 carbon atoms" described as R ⁴ to R ⁷ in the general formula (I-1) means a fat having 1 to 18 carbon atoms and which may be substituted or unsubstituted A hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an acetyl group, a hydrocarbon oxycarbonyl group, and an oxy group.

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

Examples of the aliphatic hydrocarbonoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, third butoxy, and cyclopropoxy , Cyclohexyloxy, cyclopentyloxy, allyloxy, ethyleneoxy and other aliphatic hydroxy groups with oxygen atoms bonded to the structure; these aliphatic hydrocarbon oxy groups are further alkyl, alkyl Oxygen, aryl, aryloxy, amine, hydroxy, halogen atom and other substituted groups.

Examples of the aromatic hydrocarbonoxy group include phenoxy, methylphenoxy, ethylphenoxy, methoxyphenoxy, butoxyphenoxy, phenoxyphenoxy, etc. The oxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group; these aromatic hydrocarbon oxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, halogen atoms, and the like.

Examples of the acyl group include aliphatic hydrocarbon carbonyl groups such as methyl acetyl group, ethyl acetyl group, ethyl carbonyl group, butyl acetyl group, cyclohexyl carbonyl group, and allyl carbonyl group, phenyl carbonyl group, and methyl phenyl carbonyl group Carbonyl groups, etc.; groups in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, halogen atoms, etc.

Examples of the hydrocarbon oxycarbonyl group include aliphatic methoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group, phenoxycarbonyl group, and methyl group Phenoxycarbonyl and other aromatic hydrocarbon oxycarbonyl groups, these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted by alkyl, alkoxy, aryl, aryloxy, amine, halogen atoms, etc. Base etc.

Examples of the acyloxy group include aliphatic carbonyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy, and cyclohexylcarbonyloxy groups, and phenyl groups. Carbonyloxy, methylphenylcarbonyloxy and other aromatic hydrocarbon carbonyloxy, these aliphatic hydrocarbon carbonyloxy or aromatic hydrocarbon carbonyloxy are further alkyl, alkoxy, aryl, aryloxy, Substituted groups such as amine groups and halogen atoms.

The term “two or more R ⁴ to R ⁷ may be bonded to each other to form a ring structure” as described in R ⁴ to R ⁷ of the general formula (I-1) means 2 to 4 R ⁴ to The R ⁷ bond can form an organic group of 2 to 4 valences as a whole. Examples of R ⁴ to R ⁷ at this time include alkylene groups such as ethylidene groups, propyl groups, butyl groups, pentyl groups, and hexyl groups, ethynyl groups, propynyl groups, and butynyl groups. Arylene groups such as alkenyl groups, methylene phenylene groups, phenylene groups, phenylene groups, naphthyl groups, anthracenyl groups and other aryl groups such as substituents that can form a cyclic structure, these oxy groups or dioxy groups, etc. . These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, hydroxyl groups, halogen atoms, and the like.

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

In the general formula (I-1), it is more preferable that two or more of R ¹ to R ³ are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and all of R ⁴ to R ⁷ are hydrogen At least one atom is a hydroxyl group, and the rest are all hydrogen atoms. Further preferably, all of R ¹ to R ³ are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, all of R ⁴ to R ⁷ are hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atom.

From the viewpoint of rapid hardenability, the specific hardening accelerator is preferably a compound represented by the following general formula (I-2).

[化25]

In formula (I-2), R ¹ to R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, two or more of R ¹ to R ³ may be bonded to each other to form a ring structure, and R ⁴ to R ⁶ Each is 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 ring structure.

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

Specific examples of the specific hardening accelerator include: an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, and tricyclohexyl group Addition reaction of phosphine with 1,4-benzoquinone, addition reaction of dicyclohexylphenylphosphine with 1,4-benzoquinone, addition reaction of cyclohexyldiphenylphosphine with 1,4-benzoquinone Compounds, triisobutylphosphine and 1,4-benzoquinone addition reaction product, tricyclopentylphosphine and 1,4-benzoquinone addition reaction product, etc.

The specific hardening accelerator can be obtained as an adduct of a third phosphine compound and a quinone compound, for example. Specific examples of the third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, and tri( 4-methylphenyl)phosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(isopropylphenyl) Phosphine, tri(third butylphenyl) phosphine, tri(2,4-dimethylphenyl) phosphine, tri(2,6-dimethylphenyl) phosphine, tri(2,4,6-tri Methylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine Wait. From the viewpoint of formability, triphenylphosphine and tributylphosphine are preferred.

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

The curable resin composition may contain a curing accelerator other than the phosphonium compound. Specific examples of hardening accelerators other than phosphonium compounds include 1,5-diazabicyclo[4.3.0]nonene-5 (1,5-Diazabicyclo[4.3.0]nonene-5, DBN), 1,8-Diazabicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU) and other diazabicycloalkenes, 2-methylimidazole, 2- Cyclic amidine compounds such as phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol of the cyclic amidine compounds or derivatives thereof Novolac salt; add maleic anhydride, 1,4-benzoquinone, 2,5-toluone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- to these compounds Dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4- Compounds with intramolecular polarization formed by quinone compounds such as benzoquinone and compounds with a π bond such as diazophenylmethane; tetraphenylboron salt of DBU, tetraphenylboron salt of DBN, 2-ethyl-4 -Cyclic amidinium compounds such as tetraphenylboronium salt of methylimidazole, tetraphenylboronium salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine , Tertiary amine compounds such as dimethylaminoethanol and tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, acetic acid Ammonium salt compounds such as tetraethylammonium, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide.

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

When the curable resin composition contains a curing accelerator, the amount of the curing accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass relative to 100 parts by mass of the resin component. If 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 to cure well in a short time. If the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, there is a tendency that a good molded product whose curing speed is not too fast can be obtained.

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

The type of inorganic filler is not particularly limited. Specific examples include: fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide , Zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of the inorganic filler having a flame-retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxides of magnesium and zinc, and zinc borate. Among them, from the viewpoint of a decrease in the linear expansion coefficient, molten silica is preferred, and from the viewpoint of high thermal conductivity, alumina is preferred. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of the state of the inorganic filler include powder, granules, and fibers that spheroidize the powder.

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

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, and more preferably 0.5 μm to 5 μm. If the volume average particle diameter is 0.2 μm or more, there is a tendency that the increase in the viscosity of the resin composition for molding primer is further suppressed. If the volume average particle diameter is 10 μm or less, the filling ability to narrow gaps tends to be further improved. The volume average particle diameter of the inorganic filler can be measured in the form of volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.

The volume average particle size of the inorganic filler in the curable resin composition or its cured product can be measured by a known method. For example, an inorganic filler is extracted using a self-curing resin composition or hardened material such as an organic solvent, nitric acid, aqua regia, etc., and fully dispersed by an ultrasonic disperser to prepare a dispersion liquid. Using this dispersion, the volume average particle size of the inorganic filler can be measured based on the volume-based particle size distribution measured by the laser diffraction scattering particle size distribution measuring device. Alternatively, the cured product can be embedded in a transparent epoxy resin or the like, and polished to obtain a cross section, and the volume average of the inorganic filler can be measured from the volume-based particle size distribution obtained by observing the obtained cross section with a scanning electron microscope. Particle size. Furthermore, it can also be measured by continuously performing a two-dimensional cross-sectional observation of a cured product using a FIB device (focused ion beam SEM) or the like, and performing a three-dimensional structural analysis.

From the viewpoint of the fluidity of the curable resin composition, regarding the particle shape of the inorganic filler, the spherical shape is superior to the angular shape, and it is preferable that the particle size distribution of the inorganic filler is distributed over a wide range.

[Various additives] The curable resin composition may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, and stress relievers exemplified below in addition to the above-mentioned components. In addition to the additives exemplified below, the curable resin composition may contain various additives well known in the technical field as necessary.

(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 silane-based compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, urea silane, and vinyl silane, titanium compounds, aluminum chelate compounds, and aluminum/zirconium compounds. And other well-known coupling agents.

When the curable resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the inorganic filler, and more preferably 0.1 to 2.5 parts by mass. 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. If the amount of the coupling agent is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

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

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, there is no particular limitation as long as the content of the ion exchanger is a sufficient amount for capturing ions such as halogen ions. For example, it is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the resin component, and more preferably 1 to 15 parts by mass.

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

When the curable resin composition contains a mold release agent, the amount of the mold release agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the resin component. . If the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that the mold releasability can be sufficiently obtained. If it is 15 parts by mass or less, there is a tendency to obtain better adhesion.

(Flame retardant) The curable resin composition may contain a flame retardant. The flame retardant is not particularly limited, and known ones can be used. Specifically, an organic compound or an inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, a metal hydroxide, or the like can be mentioned. One kind of flame retardant may be used alone, or two or more kinds may be used in combination.

In the case where the curable resin composition contains a flame retardant, there is no particular limitation as long as the amount of the flame retardant is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 300 parts by mass with respect to 100 parts by mass of the resin component, and more preferably 2 parts by mass to 150 parts by mass.

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

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

(Preparation method of curable resin composition) The method for preparing the curable resin composition is not particularly limited. As a general method, there can be mentioned a method in which the components of a predetermined formulation amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a grinding roll, an extruder, etc., cooled and pulverized. More specifically, for example, a method of uniformly stirring and mixing a predetermined amount of the above-mentioned components, kneading and cooling by a kneader, roller, extruder, etc. previously heated to 70° C. to 140° C. Smash.

The curable resin composition is preferably solid at normal temperature and pressure (for example, at 25° C. and atmospheric pressure). The shape of the curable resin composition when it is solid is not particularly limited, and examples thereof include powder, granule, and sheet. From the viewpoint of operability, the size and quality when the curable resin composition is in the form of a sheet are preferably a size and quality compatible with the molding conditions of the package.

<Electronic parts device> An electronic component device according to an embodiment of the present disclosure includes: an element; and a cured product of the curable resin composition that seals the element. Examples of electronic component devices include those obtained by sealing an element portion with a curable resin composition, the element portion being a lead frame, a wiring conveyor tape, a wiring board, glass, a silicon wafer, an organic substrate, etc. It is obtained by mounting components (active components such as semiconductor wafers, transistors, diodes, and gates, passive components such as capacitors, resistors, and coils) on the support member. More specifically, there may be mentioned: Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), small outline package (Small Outline Package, SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have components fixed to the lead frame and wire bonding, bumps, etc. to connect the terminal parts and lead parts of the bonding pad and other components, using a curable resin composition and by Sealing structure such as transfer molding; tape carrier package (TCP), which has a structure in which components connected to the carrier tape with bumps are sealed with a curable resin composition; Chip On Board , COB) modules, hybrid ICs, polycrystalline modules, etc., which have a curable resin composition to seal the components on the wiring formed on the support member by wire bonding, flip chip bonding, solder, etc. Structure; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which has a surface on the back side of the support member forming wiring board connection terminals The component is mounted thereon, and the component is connected to the wiring formed on the support member by bumps or wire bonding, and then the structure of the component is sealed with a curable resin composition. In addition, a curable resin composition can also be preferably used in a printed wiring board.

Examples of methods for sealing electronic component devices using a curable resin composition include low-pressure transfer molding, injection molding, and compression molding. Of these, the low-pressure transfer molding method is usually used. [Example]

Hereinafter, the embodiments will be specifically described by way of examples, but the scope of the embodiments is not limited to these examples.

[Preparation of curable resin composition] The following materials were mixed with the composition (parts by mass) described in Tables 1 to 3, and roll kneading was performed under the conditions of a kneading temperature of 80° C. and a kneading time of 15 minutes, thereby preparing Examples 1 to Examples 21. The curable resin compositions of Comparative Examples 1 to 10.

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

(hardener) Hardener 1: Phenol aralkyl resin with a hydroxyl equivalent of 176 and a softening point of 70°C (Meiwa Chemical Co., Ltd., trade name "MEH-7800") Hardener 2: Biphenyl skeleton phenol aralkyl resin with a hydroxyl equivalent of 199 and a softening point of 89°C (Meiwa Chemical Co., Ltd., trade name "MEH-7851")

(Triazine compound) Triazine compound 1: 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(octyloxy)-phenol ( Cytec (trade name "UV-1164") Triazine compound 2: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethyl Phenyl)oxy]-2-hydroxypropoxy]phenol (manufactured by BASF, trade name "Tinuvin 405") Triazine compound 3: 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (ADEKA Co., Ltd., Trade name "Adekastab (Adekastab) LA-F70") Triazine compound 4: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy-phenol (BASF), trade name " Tinuvin (1577)) Triazine compound 5: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol (ADEKA Co., Ltd., trade name "Adekastab LA-46") Triazine compound 6: 2-[4-[4,6-bis[(1,1'-biphenyl)-4-yl]-1,3,5-triazin-2-yl]-3-hydroxyl Phenoxy] isooctyl propionate (BASF company, trade name "Tinuvin 479") Triazine compound 7: 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd. , Reagents) 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)

(Hardening accelerator) Hardening accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler) Spherical fused silica (average particle size 17.5 μm, specific surface area 3.8 m ² /g ) (Coupling agent) Epoxy silane (γ-glycidoxypropyl trimethoxy silane) (Colorant) Carbon black (Mitsubishi Chemical Corporation, trade name "MA-100") (Release agent) Palm wax (Cera NODA Co., Ltd.)

[Table 1]

[Table 2]

[table 3]

[Evaluation of epoxy resin molding material for sealing] The characteristics of the epoxy resin molding material for sealing prepared 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 to 6 below. Furthermore, as long as it is not indicated, the molding of the epoxy resin molding material for sealing is performed by a transfer molding machine at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. In addition, post-curing is performed under conditions of 175°C and 5 hours as needed.

(1) Swirl Using a mold for swirling flow measurement according to EMMI-1-66, the epoxy molding material for sealing was molded under the conditions described above, and the flow distance (cm) was obtained.

(2) Hardness at hot time The epoxy resin molding material for sealing was molded into a circular plate with a diameter of 50 mm × a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness tester (made by Ueshima Manufacturing Co., Ltd., HD-1120 (D type) )) to measure.

(3) Shear adhesion at 260℃ Under the above conditions, the sealing epoxy resin molding material is formed on a silver-plated copper plate with a bottom diameter of 4 mm, an upper surface diameter of 3 mm, and a height of 4 mm, and post-hardening is performed under the conditions. After that, using a Bondtester (Series 4000 manufactured by Nordson advanced Technology Co., Ltd.), the temperature of the copper plate was maintained at 260°C and the shear was obtained at a shear rate of 50 μm/s. Then the force (MPa).

(4) Water absorption rate Post-hardening the circular plate formed in (2) under the conditions. After that, the obtained circular plate was left for 168 hours under the conditions of 85° C. and 60% RH (relative humidity), and the change in mass before and after the leaving was measured. Based on the measurement result, the water absorption rate was calculated by the following formula. Water absorption rate (mass %) = (quality of circular plate after placement-quality of circular plate before placement)/quality of circular plate before placement × 100

(5) Reflow resistance For 80-pin flat package (QFP) with a 20 mm×14 mm×2 mm outline mounted on a 8 mm×10 mm×0.4 mm silicon wafer (lead frame material: copper alloy, the upper surface of the wafer pad and the lead front plating Silver treated product), molded using the epoxy resin molding material for sealing under the above conditions, and post-hardened under the above conditions. The obtained package was humidified under the conditions of 85° C. and 85% RH for 168 hours. Afterwards, reflow soldering was performed at a prescribed temperature (250°C, 260°C, 270°C) for 10 seconds respectively to visually observe the presence or absence of cracks on the outside of the package, and an ultrasonic flaw detection device (Hitachi Construction Machinery Co., Ltd. (Manufactured by the company, HYE-FOCUS) Observe whether there is peeling inside the package. The solder reflow resistance was evaluated as the sum of the number of cracks and peelings relative to the number of test packages (10).

[Table 4]

[table 5]

[Table 6]

As shown in Tables 4 to 6, Examples 1 to 21 containing the triazine compound 1 to triazine compound 10 corresponding to the specific triazine compound are compared with Comparative Examples 1 to 8 without the triazine compound , The adhesion to metal (silver) is improved, and the reflow resistance is also improved. In Comparative Examples 9 and 10 containing the triazine compound A and the triazine compound B that are not equivalent to the specific triazine compound, compared with Comparative Examples 1 to 8 without the triazine compound, no metal (silver) was observed. ) The adhesion and reflow resistance are improved.

no

no

Claims (13)

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

[In the general formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon group] The curable resin composition according to item 1 of the patent application scope, wherein 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 selected from 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 amine group, and an aromatic group A monovalent group in the group consisting of an aliphatic hydrocarbon amine group, an aliphatic hydrocarbon amine group, a diaromatic hydrocarbon amine group, a dialiphatic hydrocarbon amine group, and an aromatic hydrocarbon aliphatic hydrocarbon amine group; n is independently 0 Integer of ~5]. The curable resin composition according to item 2 of the patent application scope, wherein at least one of the R ⁴ to R ⁶ is a hydroxyl group. The curable resin composition according to any one of claims 1 to 3, further comprising an inorganic filler. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin contains an epoxy resin. The curable resin composition according to item 5 of the patent application scope, wherein the epoxy resin comprises a resin selected from the group consisting of biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, and It consists of sulfur atom epoxy resin, novolac epoxy resin, dicyclopentadiene epoxy resin, triphenylmethane epoxy resin, copolymer epoxy resin and aralkyl epoxy resin At least one of the group. The curable resin composition according to any one of claims 1 to 6, further comprising a curing agent. The curable resin composition according to item 7 of the patent application scope, wherein the curing agent comprises a phenolic resin selected from the group consisting of aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, and benzaldehyde At least one of the group consisting of a copolymerized phenol resin of a type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. The curable resin composition according to any one of claims 1 to 8 of the patent application scope further contains a curing accelerator. The curable resin composition according to item 9 of the patent application range, wherein the curing accelerator contains a phosphonium compound. The curable resin composition according to item 9 or 10 of the patent application scope, wherein the curing accelerator contains a compound represented by the following general formula (I-1);

[In formula (I-1), R ¹ to R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ¹ to R ³ may be bonded to each other to form a ring structure; R ⁴ to R ^{7 is} 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 ring structure]. The curable resin composition according to item 11 of the patent application scope, wherein 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 ring structure; R ⁴ to R ^{6 is} 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 ring structure]. An electronic parts device including: Components; and The cured product of the curable resin composition as described in any one of claims 1 to 12 of the patent application range that seals the element.