TWI829708B - 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 compositions and electronic components and devices

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

In recent years, with the miniaturization, weight reduction, and performance improvement of electronic equipment, the density of installation has been continuously promoted. As a result, the mainstream of electronic component devices has changed from the existing pin insertion type packaging to surface mounting type packaging such as integrated circuit (IC) and large scale integrated circuit (LSI).

The installation method of the surface mount type package is different from the existing pin insertion type package. That is, when the pins are installed on the wiring board, in the existing pin insertion type package, the pins are inserted into the wiring board and then welded from the back of the wiring board, so the package is not directly exposed to high temperature. However, in surface mount packages, the entire electronic component device is processed using a solder bath, a reflow device, etc., so the package is directly exposed to soldering temperature (reflow temperature). As a result, when the package absorbs moisture, moisture absorption causes rapid expansion of the moisture during soldering, and the vapor pressure generated acts as peeling stress, causing peeling between the components, lead frames, and other interposers and the sealing material. have This may cause package cracks, poor electrical characteristics, etc. Therefore, it is desired to develop a sealing material that is excellent in adhesion to the insert and has excellent solder heat resistance (reflow resistance).

In order to meet the above requirements, the use of a silane coupling agent as a modified material for the inorganic filler contained in the sealing material has been studied. Specifically, the use of epoxy group-containing silane coupling agents or amine group-containing silane coupling agents (for example, refer to Patent Document 1), the use of sulfur atom-containing silane coupling agents (for example, refer to Patent Document 2), and the like are studied. .

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-147939

[Patent Document 2] Japanese Patent Application Publication No. 2000-103940

However, in the method using an epoxy group-containing silane coupling agent or an 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 to metals (especially noble metals such as gold and silver) is insufficient.

In view of the above-mentioned circumstances, an 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 for solving the above problems include the following embodiments.

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

In the general formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon group.

<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).

[Chemicalization 2]

In the general formula (2), R ⁴ to R ⁶ are independently selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxygen groups, aromatic hydrocarbon oxygen groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic 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 from 0 to 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 containing 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 is selected from the group consisting of biphenyl-type epoxy resin, stilbene-type epoxy resin, diphenylmethane-type epoxy resin, Sulfur atom type epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymerized epoxy resin and at least one of the group consisting of aralkyl epoxy resins.

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

<8> The curable resin composition according to <7>, wherein the curing agent contains an aralkyl phenol resin, a dicyclopentadiene phenol resin, a triphenylmethane 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 novolak 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.

<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).

In formula (I-1), R ¹ ~ R ³ are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R ¹ ~ R ³ can be bonded to each other to form a cyclic structure; R ⁴ ~ 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 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).

In formula (I-2), R ¹ ~ R ³ are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R ¹ ~ R ³ can be bonded to each other to form a cyclic structure; R ⁴ ~ R ⁶ They 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.

<13> An electronic component device including: a component; and a hardened product of the curable resin composition according to any one of <1> to <12> that seals the component.

According to the present invention, there are 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, the form for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise expressly stated. The same applies to numerical values and their ranges, which do not limit the present invention.

In this disclosure, the term "step" includes steps other than steps that are independent from other steps, even if they cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved.

In this disclosure, in the numerical range represented by "~", the numerical values recorded before and after "~" are respectively regarded as the minimum value and the maximum value.

Among the numerical ranges described in stages in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical range described, the upper limit value or the lower limit value of this numerical range may be replaced with the value shown in the Example.

In this disclosure, the content rate or content of each component in the composition, when there are multiple substances corresponding to each component in the composition, refers to the content of the component present in the composition unless otherwise specified. The total content rate or content of multiple substances.

In this disclosure, when there are multiple types of particles corresponding to each component in the composition, the particle size of each component in the composition refers to the mixture of the multiple types of particles present in the composition unless otherwise specified. value.

<Cureable resin composition>

A curable resin composition according to one 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).

Research by the present inventors revealed that a 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 for this is not yet clear, but it is speculated that the specific triazine compound in the hardened product forms a coordination bond with the metal.

The curable resin composition containing a specific triazine compound has excellent adhesion to metal in a cured state. Therefore, when used as a sealing material for a package including a lead frame whose material at least the surface is metal, the lead frame can be suppressed from being Peeling between sealants. Therefore, the reflow resistance is excellent.

(specific triazine compounds)

The specific triazine compound is a compound represented by the following general formula (1). A single type of specific triazine compound may be used, or two or more types having different structures may be used.

[Chemistry 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. Examples include aromatic hydrocarbon groups and aliphatic hydrocarbon groups.

Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, and the like.

Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and the like.

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

Specific examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, and cyclohexenyl, adamantyl, and norbornyl. , dicyclopentyl, etc.

The monovalent hydrocarbon group represented by R ¹ to R ³ may have a substituent. Examples of the substituent include aromatic hydrocarbon group, aliphatic hydrocarbon group, aliphatic hydrocarbonoxy group, aromatic hydrocarbonoxy group, hydroxyl group, carboxyl group, halogen atom, amino group, aromatic hydrocarbon amine group, aliphatic hydrocarbon amine group, di Aromatic hydrocarbon amine group, dialiphatic hydrocarbon amine group, aromatic hydrocarbon aliphatic hydrocarbon amine group, etc.

Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, and the like.

Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and the like.

Examples of the aromatic hydrocarbon oxygen group include groups in which an oxygen atom is bonded to an aromatic hydrocarbon group such as a phenyl group or a naphthyl group.

Examples of the aliphatic hydrocarbonoxy group include groups 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 or 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, it is preferable that each independently has a carbon number of 1 to 30. When the monovalent hydrocarbon group represented by R ¹ to R ³ has a substituent, the carbon atom contained in the substituent is also included in the "carbon number of the monovalent carbon atom".

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

[Chemical 6]

In the general formula (2), R ⁴ to R ⁶ are independently selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxygen groups, aromatic hydrocarbon oxygen groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic 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 from 0 to 5.

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

In a certain 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 addition, in a certain 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.

[Chemical 7]

The amount of the specific triazine compound in the curable resin composition is not particularly limited. From the viewpoint of fully obtaining the effect of improving the adhesion to gold and silver, for example, relative to the total of the curable resin contained in the curable resin composition and the curing agent used if 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, 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.

(hardening 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, thermosetting properties are preferred. The curable resin may be one that hardens by self-polymerization, or it may be Hardened by reaction with hardeners, cross-linking agents, etc.

The functional group that reacts to produce a curable resin is not particularly limited, and examples thereof include: epoxy group, cyclic ether group such as oxetanyl group, hydroxyl group, carboxyl group, amine group, acryl group, isocyanate group, and maleic acid group. Amino group, alkenyl group, etc. From the viewpoint of the balance of properties as a sealing material, a curable resin containing a cyclic ether group is preferred, and a curable resin containing an epoxy group (epoxy resin) is more preferred.

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

Specific examples include: phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and α-naphthol, β-naphthol, bisphenol, etc. At least one phenolic compound in the group consisting of naphthol compounds such as hydroxynaphthalene and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc. are condensed or co-condensed under an acidic catalyst to obtain a novolak resin and the novolak resin Novolak-type epoxy resin (phenol novolak-type epoxy resin, o-cresol novolak-type epoxy resin, etc.) obtained by epoxidation of resin; the phenolic compound is mixed with aromatic compounds such as benzaldehyde and salicylaldehyde. Aldehyde compounds are condensed or co-condensed under an acidic catalyst to obtain a triphenylmethane-type phenol resin, and the triphenylmethane-type phenol resin is epoxidized to obtain a triphenylmethane-type epoxy resin; making the phenolic compound And a copolymerized epoxy resin obtained by co-condensing a naphthol compound and an aldehyde compound under an acidic catalyst to obtain a novolac resin and epoxidizing the novolak resin; as a disacid of bisphenol A, bisphenol F, etc. Diphenylmethane-type epoxy resins as glyceryl ethers; biphenyl-type epoxy resins as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-based phenol compounds stilbene-type epoxy resins that are diglycidyl ethers of bisphenol S, etc.; sulfur atom-containing epoxy resins that are diglycidyl ethers such as bisphenol S; epoxy resins that are alcohols such as butylene glycol, polyethylene glycol, and polypropylene glycol. Epoxy resins of glycidyl ethers; glycidyl ester type epoxy resins which are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; aniline, diamine dicarboxylic acid Glycidyl amine type epoxy resin obtained by replacing the active hydrogen bonded to the nitrogen atom of phenylmethane, isocycyanuric acid, etc. with a glycidyl group; cyclization of the co-condensation resin of dicyclopentadiene and phenolic compounds Dicyclopentadiene-type epoxy resin obtained by oxidation; diepoxidized vinylcyclohexene and 3,4-epoxycyclohexylmethyl-3,4- obtained by epoxidation of olefin bonds in the molecule Alicyclic types such as epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane Epoxy resin; p-xylene modified epoxy resin as glycidyl ether of p-xylene modified phenol resin; m-xylene modified epoxy resin as glycidyl ether of m-xylene modified phenol resin; as terpene Terpene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; dicyclopentadiene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; as cyclopentadiene-modified epoxy resin Cyclopentadiene-modified epoxy resin is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; a polycyclic aromatic ring-modified epoxy resin is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; and a phenol resin containing a naphthalene ring is used. Naphthalene-type epoxy resin of glycidyl ether; halogenated phenol novolak-type epoxy resin; hydroquinone-type epoxy resin; trimethylolpropane-type epoxy resin; obtained by oxidizing olefin bonds using peracids such as peracetic acid. linear aliphatic epoxy resin; aralkyl-type epoxy resin obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin. Furthermore, epoxides of silicone resins, acrylic resins, etc. Epoxides of resins, etc. are used as epoxy resins. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.

Among the epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, it is preferable to be selected from the group consisting of biphenyl-type epoxy resin, stilbene-type epoxy resin, and diphenylmethane-type epoxy resin. , sulfur atom-containing epoxy resin, novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenylmethane-type epoxy resin, copolymerized epoxy resin and aralkyl-type epoxy resin Epoxy resins in the group consisting of (referred to as "specific epoxy resins"). A specific epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

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

From the viewpoint of fluidity, among the specific epoxy resins, biphenyl-type epoxy resin, stilbene-type epoxy resin, diphenylmethane-type epoxy resin or sulfur atom-containing epoxy resin is more preferred in terms of heat resistance. From the viewpoint of stability, dicyclopentadiene-type epoxy resin, triphenylmethane-type epoxy resin or aralkyl-type epoxy resin is preferred. Specific examples of preferred epoxy resins are shown below.

The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred. In the epoxy resin represented by the following general formula (II), when the positions where the oxygen atom in R ⁸ is substituted is the 4-position and the 4'-position, the 3, 3', 5, and 5' positions are methyl groups and in addition YX-4000H (trade name, Mitsubishi Chemical Co., Ltd.) in which R ⁸ is a hydrogen atom, and 4,4'-bis(2,3-epoxypropoxy)biphenyl in which all R ⁸ are hydrogen atoms. , in all cases where R ⁸ is a hydrogen atom and when the oxygen atom in R ⁸ is substituted at the 4-position and 4'-position, the 3, 3', 5, and 5' positions are methyl groups, and the other R ⁸ In the case of a hydrogen atom, a mixture such as YL-6121H (trade name of Mitsubishi Chemical Co., Ltd.) is available as a commercial product.

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

The stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferred. In the epoxy resin represented by the following general formula (III), when the positions where the oxygen atom in R ⁹ is substituted are the 4-position and the 4'-position, the 3, 3', 5, and 5' positions are methyl groups and in addition Except for the case where R ⁹ is a hydrogen atom and R ¹⁰ are all hydrogen atoms, and among R ⁹ , 3 of the 3, 3', 5, and 5' positions are methyl and 1 is the tert-butyl group, and other than A mixture product in which R ⁹ is a hydrogen atom and R ¹⁰ are both hydrogen atoms, namely ESLV-210 (trade name of Sumitomo Chemical Co., Ltd.), is available as a commercial product.

[Chemical 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, representing a number from 0 to 10.

The diphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferred. In the epoxy resin represented by the following general formula (IV), R ¹¹ is a hydrogen atom, and the position where the oxygen atom in R ¹² is substituted is 3, 3', 5, 5' when the 4-position and 4'-position are YSLV-80XY (trade name, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), in which R ¹² is a methyl group and the other R 12 is a hydrogen atom, is available as a commercial product.

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, representing a number from 0 to 10.

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing sulfur atoms. Examples thereof include epoxy resins represented by the following general formula (V). In the epoxy resin represented by the following general formula (V), when the positions where the oxygen atom in R ¹³ is substituted are the 4-position and the 4'-position, the 3,3'-position is the tert-butyl group and the 6,6'-position YSLV-120TE (trade name, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) in which R ¹³ is a methyl group and the other R 13 is a hydrogen atom is available as a commercial product.

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

The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak-type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolac resin, a cresol novolac resin, and a naphthol novolac resin using a method such as glycidyl etherification is preferred, and more preferably the following general Epoxy resin represented by formula (VI). In the epoxy resin represented by the following general formula (VI), all R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, and i=1, ESCN-190 and ESCN-195 (trade name of Sumitomo Chemical Co., Ltd.); N- ⁷⁷⁰ and N-775 (trade name of DIC Co., Ltd.) in which all R 14 are hydrogen atoms and i=0; the part in which all R ¹⁴ are hydrogen atoms and i=0 is the same as i=1, A styrene-modified phenol novolak-type epoxy resin in which R ¹⁵ is -CH(CH ₃ )-Ph, that is, YDAN-1000-10C (trade name of Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); as having R Benzyl modified cresol novolak type epoxy resin where all ¹⁴ are hydrogen atoms, i=1, ^R15 is methyl group and i=2, one of ^R15 is methyl group and one is benzyl group , that is, HP-5600 (trade name of DIC Co., Ltd.) and the like are available as commercial products.

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

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

[Chemical 13]

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

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

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. i independently represents an integer from 0 to 3, and k represents an integer from 0 to 4 independently. n is the average value, representing a number from 0 to 10.

The copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound may be an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. , there are no special restrictions. For example, an epoxy resin obtained by glycidyl etherification of a novolak-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Oxygen resin. Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name of Nippon Kayaku Co., Ltd., trade name), etc., in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0, can be used. Obtained from commercially available products.

In formula (IX), R ¹⁹ to R ²¹ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3, j independently represents an integer from 0 to 2, and k represents an integer from 0 to 4 independently. l and m are respectively the average value and a number from 0 to 10, and (l+m) represents a number from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either formula (IX-1) or formula (IX-2) below. In formula (IX-1) and formula (IX-2), the definitions of i, j and k in R ¹⁹ ~ R ²¹ are the same as the definitions of i, j and k in R ¹⁹ ~ R ²¹ in formula (IX). same. n is 1 (when bonding via a methylene group) or 0 (when bonding is not via a methylene group).

Examples of the epoxy resin represented by the general formula (IX) include a random copolymer including one structural unit and m structural units randomly, and a random copolymer including one structural unit and m structural units alternately. Alternating copolymers, copolymers including one structural unit and m structural units regularly, block copolymers including one structural unit and m structural units in block form, etc. Any one of these may be used alone, or two or more types may be used in combination.

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

The 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 dimethylnaphthol, and is composed of dimethoxy-dimethoxy The epoxy resin using a phenol resin synthesized from toluene, bis(methoxymethyl)biphenyl or their derivatives as a raw material is not particularly limited. For example, it is preferable to combine at least one compound selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol with dimethoxy-p-xylene, bis(methoxy-p-xylene, etc.) An epoxy resin obtained by glycidyl etherification of a phenol resin synthesized from methyl)biphenyl or these derivatives is more preferably represented by the following general formula (X) and general formula (XI) of epoxy resin.

In the epoxy resin represented by the following general formula (X), in which i is 0 and R ³⁸ is a hydrogen atom, NC-3000S (trade name of Nippon Kayaku Co., Ltd.) is used, with i being 0 at a mass ratio of 80:20. In addition, CER-3000 (trade name of Nippon Kayaku Co., Ltd.), which is a mixture of an epoxy resin in which R ³⁸ is a hydrogen atom and an epoxy resin in which all R ⁸ is a hydrogen atom in the general formula (II), is available on the market. Obtained from the sale of goods. In addition, among the epoxy resins represented by the following general formula (XI), ESN-175 (trade name of Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc., in which i is 0, j is 0, and k is 0, is commercially available as Obtained by product.

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 monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i is an integer from 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 4, and l is an integer from 0 to 6. n is the average value, each 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 "can be the same or different" means, for example, 8 ~ in the formula (II). The 88 R ^8s can all be the same or different. Regarding the other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ , 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, respectively. For example, R ⁹ and R ¹⁰ may both be the same or different.

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

n in the general formulas (II) to (XI) is an average value, preferably in the range of 0 to 10 independently. 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 filling defects, deformation of bonding wires (metal wires connecting components and leads), etc. will be suppressed. tendency. It is more preferable that n is set in the range of 0~4.

The functional group equivalent of the curable resin (epoxy equivalent in the case of epoxy resin) is not particularly limited. From the viewpoint of balancing various characteristics such as formability, reflow resistance, and electrical reliability, the functional group equivalent weight of the curable resin is preferably 100g/eq~1000g/eq, and more preferably 150g/eq~500g/eq.

The softening point or melting point of the curable resin is not particularly limited. From the viewpoint of formability and reflow resistance, 40°C to 180°C is preferred, and from the viewpoint of workability during preparation of the curable resin composition, 50°C to 130°C is more preferred.

From the viewpoints of strength, fluidity, heat resistance, formability, etc., the curable resin content 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 also 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 properties of the curable resin composition, and the like.

When the curable resin is an epoxy resin, examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, and block isocyanate curing agents. Agents, etc. From the viewpoint of both hardening properties and pot life, at least one selected from the group consisting of phenol hardeners, amine hardeners and acid anhydride hardeners is preferred, and from the viewpoint of electrical reliability, it is more preferred Phenol hardener.

Examples of the phenol curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol may be listed; selected from the group consisting of phenol, cresol, and xylenol. , resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenol compounds and α-naphthol, β-naphthol, dihydroxynaphthol and other naphthol compounds A novolac-type phenolic resin obtained by condensing or co-condensing at least one phenolic compound in the group with formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and other aldehyde compounds under an acidic catalyst; made from the phenol Aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin synthesized from chemical 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 synthesized by copolymerization of the phenolic compound and dicyclopentadiene Diene-type phenol resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; making the phenolic compound and benzaldehyde, Triphenylmethane-type phenol resin obtained by condensation or co-condensation of aromatic aldehyde compounds such as salicylaldehyde under an acidic catalyst; phenol resin obtained by copolymerizing two or more of these, etc. These phenol hardeners may be used individually by 1 type, or in combination of 2 or more types.

Among the phenol hardeners, from the viewpoint of reflow resistance, it is preferable to select one selected from the group consisting of aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, benzaldehyde type phenol resin and 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 referred to as "specific phenol hardeners"). A specific phenol hardener may be used individually by 1 type, and may be used in combination of 2 or more types.

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

Examples of the aralkyl-type phenol resin include phenol aralkyl resin, naphthol aralkyl resin, etc. synthesized from a phenolic compound and dimethoxyp-xylene, bis(methoxymethyl)biphenyl, etc. . Aralkyl phenol resins can also be copolymerized with other phenol resins. Examples of the copolymerized aralkyl phenol resin include a copolymerized phenol resin of a benzaldehyde phenol resin and an aralkyl phenol resin, a copolymerized salicylaldehyde phenol resin and an aralkyl phenol resin. Phenol resin, copolymerized phenol resin of novolak type phenol resin and aralkyl type phenol resin, etc.

The aralkyl-type phenol resin is composed of at least one selected from the group consisting of phenol compounds and naphthol compounds, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof. The phenol resin synthesized is not particularly limited. For example, phenol resins represented by the following general formulas (XII) to (XIV) are preferred.

In formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and 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. 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. i is an integer from 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 4, and p is an integer from 0 to 4. n is the average value, each independently a number from 0 to 10.

Among the phenol resins represented by the general formula (XII), MEH-7851 (trade name of Meiwa Kasei Co., Ltd.) in which i is 0 and R ²³ is a hydrogen atom is available as a commercial product.

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

In the phenol resin represented by the general formula (XIV), j is 0, k is 0, and p is 0, SN-170 (trade name of Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), j is 0, and k is 1 , SN-395 (trade name, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) in which R ²⁷ is a hydroxyl group and p is 0 is available as a commercial 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, a phenol resin represented by the following general formula (XV) is preferred. Among the phenol resins represented by the following general formula (XV), DPP (trade name of New Nippon Petrochemical Co., Ltd.), etc., in which i is 0, are available as commercial products.

In formula (XV), R ²⁹ represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3. n is the average value, representing a number from 0 to 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, a phenol resin represented by the following general formula (XVI) is preferred.

Among the phenol resins represented by the following general formula (XVI), MEH-7500 (trade name of Meiwa Kasei Co., Ltd.) in which i is 0 and k is 0 is available as a commercial product.

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 an integer from 0 to 3 independently, and k is an integer from 0 to 4 independently. n is the average value, which is a number from 0 to 10.

The copolymer-type phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin can be used as long as it is a copolymer-type phenol resin of a phenol resin and an aralkyl-type phenol resin obtained by using a compound having a benzaldehyde skeleton as a raw material. No special restrictions. For example, a phenol resin represented by the following general formula (XVII) is preferred.

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

In formula (XVII), R ³² to R ³⁴ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i is an integer from 0 to 3, k is an integer from 0 to 4, and q is an integer from 0 to 5. l and m are respectively average values, and are independently numbers from 0 to 11. Among them, the total 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 phenol compounds and naphthol compounds and an aldehyde compound under an acidic catalyst. limited. For example, a phenol resin represented by the following general formula (XVIII) is preferred.

Among the phenol resins represented by the following general formula (XVIII), Tamanol 758 and ⁷⁵⁹ (trade name of Arakawa Chemical Industry Co., Ltd.), HP-850N ( Hitachi Chemical Co., Ltd., trade name) and the like are available as commercial products.

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

The words "may be the same or different" described in the R ²² to R ³⁶ in the general formula (XII) to the general formula (XVIII), for example, means that i R ²² in the formula (XII) may be all the same or different. different from each other. Regarding the other R ²³ to R ³⁶ , it means that the respective numbers contained 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, respectively. 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.

n in the general formulas (XII) to (XVIII) 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, the viscosity of the curable resin composition during melt molding will also be low, and filling defects will not occur or bonding wires (metal wires that connect components and leads) will not easily occur. Deformation. average in 1 molecule n 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 the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 70g/eq to 1000g/eq is preferred, and 80g/eq to 500g/eq is more preferred.

The softening point or melting point of the hardener is not particularly limited. From the viewpoint of formability and reflow resistance, 40°C to 180°C is preferred, and from the viewpoint of workability during production of the curable resin composition, 50°C to 130°C is more preferred.

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 (number of functional groups in the curing agent/number of functional groups in the curing resin) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small amount, it is preferably set to the range of 0.5 to 2.0, and more preferably set to the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

(hardening accelerator)

The curable resin composition may also 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 properties of the curable resin composition, and the like.

From the viewpoint of hardening properties and fluidity, the hardening accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-toluene)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, and tris(alkyl.alkoxy)phosphine. phenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, Tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl Tertiary phosphine such as phosphine; maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone , 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds A compound with intramolecular polarization formed by the addition of compounds with π bonds such as diazophenylmethane; in making the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2- Bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methyl phenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1 -Naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and other halogenated phenol compounds are obtained through the dehydrohalogenation step and have intramolecular properties. Polarized compounds; tetraphenylphosphonium and other tetrasubstituted phosphoniums, tetra-p-toluene borate and other tetrasubstituted phosphoniums and tetrasubstituted borates that do not have a phenyl group bonded to the boron atom; tetrasubstituted phosphoniums and phenolic compounds that are free of protons The salt of the anion after the tetrasubstituted phosphonium and the anion after removing the proton from the carboxylic acid compound, etc.

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

[Chemistry 24]

In formula (I-1), R ¹ ~ R ³ are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R ¹ ~ R ³ can be bonded to each other to form a cyclic structure. R ⁴ ~ 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 cyclic 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 carbon atoms, and even 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 may be 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.

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

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

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

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

The term "two or more of R ¹ to R ³ may be bonded to each other to form a cyclic structure" described as R ¹ to R ³ in the general formula (I-1) means two of R ¹ to R ³ Or three bonds, the whole becomes a divalent or trivalent hydrocarbon group. Examples of R ¹ to R ³ at this time include alkylene groups such as ethylene group, propylene group, butylene group, pentylene group, and hexylene group, which can be bonded to a phosphorus atom to form a cyclic structure. Alkenylene groups such as ethynyl, propynyl and butynyl groups, aralkyl groups such as methylene phenylene group, arylyl groups such as phenylene group, naphthylene group, anthracenyl group, etc., can be combined with phosphorus atoms A substituent that bonds to form a cyclic structure. These substituents may also be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

The "organic group having 1 to 18 carbon atoms" described as R ⁴ to R ⁷ in the general formula (I-1) refers to a fat containing 1 to 18 carbon atoms that may or may not be substituted. aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbonoxy group, aromatic hydrocarbonoxy group, acyl group, alkoxycarbonyl group, and acyloxy group.

Examples of the aliphatic hydrocarbon group and 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 .

Examples of the aliphatic hydrocarbonoxy group include: methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, tert-butoxy group, and cyclopropoxy group , cyclohexyloxy, cyclopentyloxy, allyloxy, vinyloxy and other aliphatic hydrocarbon groups with oxygen atoms bonded to the structure of the structure; these aliphatic hydrocarbon oxygen groups are further alkyl, alkyl Substituted groups such as oxygen group, aryl group, aryloxy group, amine group, hydroxyl group, halogen atom, etc.

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

Examples of the hydroxyl group include aliphatic hydrocarbon carbonyl groups such as a formyl group, acetyl carbonyl group, ethyl carbonyl group, butyl carbonyl group, cyclohexyl carbonyl group, and allyl carbonyl group, and aromatic hydrocarbon groups such as a phenyl carbonyl group and methylphenyl carbonyl group. Carbonyl groups, etc.; these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, halogen atoms, etc.

Examples of the hydrocarbonoxycarbonyl group include aliphatic hydrocarbonoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, and cyclohexyloxycarbonyl group; Aromatic hydrocarbonoxycarbonyl groups such as phenoxycarbonyl group and methylphenoxycarbonyl group, these aliphatic hydrocarbonoxycarbonyl groups or aromatic hydrocarbonoxycarbonyl groups are further substituted by alkyl group, alkoxy group, aryl group, aryloxy group, amine group, Substituted groups such as halogen atoms and the like.

Examples of the hydroxyl group include aliphatic hydrocarbon carbonyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy, cyclohexylcarbonyloxy, and the like, and phenyl Aromatic hydrocarbon carbonyloxy groups such as carbonyloxy and methylphenylcarbonyloxy, these aliphatic hydrocarbon carbonyloxy or aromatic hydrocarbon carbonyloxy groups are further substituted by alkyl, alkoxy, aryl, aryloxy, Substituted groups such as amine group and halogen atom, etc.

The term "two or more R ⁴ to R ⁷ can 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 to R ⁷ bond, as a whole can form a 2- to 4-valent organic group. Examples of R ⁴ to R ⁷ in this case include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, and alkylene groups such as ethynyl, propynyl, and butynyl. arylalkylene groups such as alkenyl and methylene phenylene groups, arylalkylene groups such as phenylene groups, naphthylene groups, and anthracenyl groups, and other substituents that can form a cyclic structure, and their oxy or dioxy groups, etc. . These substituents may also be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

R ⁴ to R ⁷ in the general formula (I-1) are not particularly limited. For example, it is preferable to be independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkoxy group. Substituted aryloxy. Among them, from the viewpoint of easy acquisition of raw materials, a hydrogen atom, a hydroxyl group, an aryl group that is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a chain Shape or cyclic alkyl group. Examples of the aryl group that is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include phenyl, p-tolyl, m-tolyl, o-tolyl, and p-methoxybenzene Key et al. Examples of the chain or cyclic alkyl group include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, tert-butyl, octyl, cyclohexyl, and the like. From the viewpoint of hardenability, it is preferable that all R ⁴ to R ⁷ are hydrogen atoms, or that at least one of R ⁴ to R ⁷ is a hydroxyl group and the rest are all hydrogen atoms.

In 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 R ⁴ to R ⁷ are hydrogen. At least one of the atoms is a hydroxyl group, and all the others are hydrogen atoms. More preferably, all of R ¹ to R ³ are alkyl groups with 1 to 18 carbon atoms or cycloalkyl groups with 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 atoms. atom.

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

In formula (I-2), R ¹ ~ R ³ are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R ¹ ~ R ³ can be bonded to each other to form a cyclic structure. R ⁴ ~ R ⁶ They 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.

Specific examples of R ¹ to R ⁶ in the general formula (I-2) are the same as those of R ¹ to R ⁶ in the general formula (I-1), 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 Addition reaction product of phosphine and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction of cyclohexyldiphenylphosphine and 1,4-benzoquinone substance, the addition reaction product of triisobutylphosphine and 1,4-benzoquinone, the addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone, etc.

Specific hardening accelerators are available, for example, as adducts of third phosphine compounds and quinone compounds.

Specific examples of the third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris( 4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylphenyl) Phosphine, tris(tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-tris Methylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(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, Diphenoquinone, 1,4-naphthoquinone, anthraquinone, etc. 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 (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, and 2-heptadecylimidazole; derivatives of the cyclic amidine compound; phenol of the cyclic amidine compound or its derivatives Novolac salt; maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4- Compounds with intramolecular polarization formed from quinone compounds such as benzoquinone and compounds with π bonds such as diazophenylmethane; DBU tetraphenylboron salt, DBN tetraphenylboron salt, 2-ethyl-4 - Cyclic amidinium compounds such as tetraphenylboron salt of methylimidazole and tetraphenylboron salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, and triethanolamine , dimethylaminoethanol, tris(dimethylaminomethyl)phenol and other tertiary amine compounds; 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, tetrapropylammonium hydroxide, etc.

The curable resin composition contains a specific hardening accelerator as a hardening accelerator. When adding an agent, the content rate of the specific hardening accelerator is preferably 30 mass% or more of the entire hardening accelerator, more preferably 50 mass% or more, and still more preferably 70 mass% or more.

When the curable resin composition contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 to 30 parts by mass, and 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 for good curing in a short time. When the amount of the curing accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, a good molded article in which the curing speed is not too fast tends to be obtained.

(Inorganic filler material)

The curable resin composition may contain an inorganic filler. Particularly 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, and zirconium oxide. , zircon, forsterite, talc, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc composite hydroxides, zinc borate, and the like. Among them, from the viewpoint of reducing the linear expansion coefficient, fused silica is preferred, and from the viewpoint of high thermal conductivity From a viewpoint, 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, particles obtained by spheroidizing the powder, and fibers.

When the curable resin composition contains an inorganic filler, its content rate is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30 volume % to 90 volume % of the entire curable resin composition, more preferably 35 volume % to 80 volume %, and still more preferably 40 volume % to 70 volume %. If the content rate of the inorganic filler is 30 volume % or more of the entire curable resin composition, properties such as thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to further improve. When the content rate of the inorganic filler is 90 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 become better.

The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 0.2 μm to 10 μm, more preferably 0.5 μm to 5 μm. If the volume average particle diameter is 0.2 μm or more, an increase in the viscosity of the resin composition for mold primers tends to be further suppressed. When the volume average particle diameter is 10 μm or less, the filling property of narrow gaps tends to be further improved. The volume average particle diameter of the inorganic filler can be measured as the volume average particle diameter (D50) using a laser diffraction scattering particle size distribution measuring device.

The volume average particle diameter of the inorganic filler in the curable resin composition or its cured product can be measured by a known method. For example, organic solvents, nitric acid, aqua regia and other self-curing resin compositions or hardened materials are used to extract inorganic fillers. Disperse thoroughly using an ultrasonic disperser or the like to prepare a dispersion liquid. The volume average particle diameter of the inorganic filler can be measured based on the volume-based particle size distribution measured using a laser diffraction scattering particle size distribution measuring device using this dispersion liquid. Alternatively, the hardened material can be embedded in transparent epoxy resin, etc., polished to obtain a cross-section, and the volume-based particle size distribution obtained by observing the obtained cross-section with a scanning electron microscope can be used to measure the volume average of the inorganic filler. particle size. Furthermore, it can also be measured by continuously observing the two-dimensional cross-section of the hardened material 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, the particle shape of the inorganic filler is preferably spherical rather than angular, and it is preferable that the particle size distribution of the inorganic filler is distributed in a wide range.

[Various additives]

In addition to the above-mentioned components, the curable resin composition may also contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, and stress relaxants exemplified below. In addition to the additives exemplified below, the curable resin composition may optionally contain various additives well known in the art.

(coupling agent)

When the curable resin composition contains an inorganic filler, a coupling agent may be included in order to improve the adhesiveness between the resin component and the inorganic filler. Examples of the coupling agent include silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureasilane, and vinylsilane, titanium-based compounds, aluminum chelate compounds, and aluminum/zirconium-based 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, and more preferably 0.1 to 2.5 parts by mass relative to 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more based on 100 parts by mass of the inorganic filler, the adhesiveness to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the formability of the package tends to be further improved.

(ion exchanger)

The curable resin composition may contain an ion exchanger. In particular, when a curable resin composition is used as a sealing molding material, 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. Exchange body. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. One type of ion exchanger may be used alone, or two or more types of ion exchangers 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 to capture halogen ion plasma. For example, it 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.

(release agent)

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

When the curable resin composition contains a release agent, the amount of the release agent is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the resin component. . When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, sufficient release properties tend to be obtained. If it is 15 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardant)

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

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

(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 depending on the purpose and the like. A colorant may be used individually by 1 type, and may be used in combination of 2 or more types.

(stress reliever)

The curable resin composition may also contain stress relieving agents such as silicone oil and silicone rubber particles. By including a stress reliever, the occurrence of package warpage and package cracks can be further reduced. Examples of the stress relieving agent include commonly used known stress relieving agents (flexibility agents). Specifically, thermoplastic elastomers such as silicone type, styrene type, olefin type, urethane type, polyester type, polyether type, polyamide type, polybutadiene type, etc., 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 reliever may be used alone, or two or more types may be used in combination. Among them, silicone-based stress relieving agents are preferred. Examples of silicone-based stress relieving agents include those having an epoxy group, those having an amine group, those obtained by polyether modification, and the like.

(Preparation method of curable resin composition)

The preparation method of the curable resin composition is not particularly limited. As a general method, the following method can be cited: using a mixer, etc., to mix ingredients in a predetermined amount After mixing, the mixture is melt-kneaded using a grinding roller, an extruder, etc., then cooled and pulverized. More specifically, for example, the following method can be cited: uniformly stirring and mixing a predetermined amount of the above ingredients, kneading and cooling using a kneader, roller, extruder, etc. that has been preheated to 70°C to 140°C, and then cooling. Crush.

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

<Electronic component device>

An electronic component device according to an embodiment of the present disclosure includes: a component; and a cured product of the curable resin composition that seals the component.

Examples of electronic component devices include those obtained by sealing element portions such as lead frames, wired conveyor tapes, wiring boards, glass, silicon wafers, organic substrates, etc., with curable resin compositions. It is obtained by mounting components (active components such as semiconductor wafers, transistors, diodes, and thyristors, passive components such as capacitors, resistors, and coils, etc.) on the supporting member.

More specifically, they can be listed: 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, General resin-sealed ICs such as TSOP (TSOP) and Thin Quad Flat Package (TQFP) have components such as terminals and bonding pads that are fixed to the lead frame and connected by wire bonding, bumps, etc. After the lead part, a curable resin composition is used and sealed by transfer molding, etc.; a tape carrier package (TCP), which has a curable resin composition that is connected to the carrier tape with bumps A structure in which components are sealed; Chip On Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which use a curable resin composition to connect to the Structures that seal components on the wiring formed on the support member; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which have A structure in which components are mounted on the surface of a support member with wiring board connection terminals formed on the back side, and the components are connected to wiring formed on the support member through bumps or wire bonding, and then the components are sealed with a curable resin composition. In addition, the curable resin composition can also be preferably used in printed wiring boards.

Examples of methods for sealing electronic component devices using curable resin compositions include low-pressure transfer molding, injection molding, and compression molding. Among these, the low-pressure transfer molding method is usually used.

[Example]

Hereinafter, the embodiment will be described in detail using examples, but the scope of the embodiment is not limited to these examples.

[Preparation of curable resin composition]

The following materials were mixed with the compositions (mass parts) described in Tables 1 to 3, and roller kneading was performed at a kneading temperature of 80° C. and a kneading time of 15 minutes to prepare Examples 1 to 1. 21. The curable resin compositions of Comparative Examples 1 to 10.

(epoxy resin)

． Epoxy resin 1: biphenyl-type epoxy resin with an epoxy equivalent of 196 and a melting point of 106°C (Mitsubishi Chemical Co., Ltd., trade 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 & Sumitomo Metal Chemical Co., Ltd., trade name "YDAN-1000-10C")

Epoxy Resin 3: Methoxynaphthalene with an epoxy equivalent of 250 and a softening point of 58°C. Cresol-formaldehyde co-condensation type epoxy resin (DIC Co., Ltd., trade name "HP-5000")

． Epoxy Resin 4: Aralkyl-type epoxy resin containing an extended biphenyl 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 type 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 Corporation, 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., Product name "Adekastab LA-F70")

Triazine compound 4: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy-phenol (BASF Company, trade name " Tinuvin1577")

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-hydroxy Phenoxy]isooctylpropionate (BASF, 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. , 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)

(hardening accelerator)

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

(Inorganic filler material)

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

(coupling agent)

Epoxysilane (γ-glycidoxypropyltrimethoxysilane)

(colorant)

Carbon black (Mitsubishi Chemical Co., Ltd., trade name "MA-100")

(release agent)

Palm wax (Cera NODA Co., Ltd.)

[Evaluation of epoxy resin molding materials for sealing]

The characteristics of the sealing epoxy resin molding materials 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. In addition, unless otherwise specified, the sealing epoxy resin molding material is 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. In addition, if necessary, post-hardening is performed at 175°C for 5 hours.

(1) Swirl

Using a swirl flow measurement mold conforming to EMMI-1-66, the sealing epoxy resin molding material was molded under the conditions described above, and the flow distance (cm) was determined.

(2)Hot hardness

The sealing epoxy resin molding material was formed into a circular plate with a diameter of 50 mm x a thickness of 3 mm under the above conditions, and a Shore D type hardness tester (manufactured by Uejima Seisakusho Co., Ltd., HD-1120 (D type)) was used immediately after forming. to measure.

(3) Shear bonding strength at 260℃

Under the above conditions, the sealing epoxy resin molding material was formed on a silver-plated copper plate with a bottom surface diameter of 4 mm, an upper surface diameter of 3 mm, and a height of 4 mm, and was post-hardened under the above conditions. Thereafter, a bond tester (Bondtester) (Series 4000 manufactured by Nordson Advanced Technology Co., Ltd.) was used to determine the shear bonding strength at a shear speed of 50 μm/s while maintaining the temperature of the copper plate at 260°C. Force (MPa).

(4)Water absorption rate

The circular plate formed in (2) is post-hardened under the above conditions. Thereafter, the obtained disc was left standing for 168 hours under the conditions of 85° C. and 60% RH (relative humidity), and the mass change before and after the standing was measured. Based on the measurement results, the water absorption rate is calculated by the following formula.

Water absorption rate (mass %) = (mass of the disc after placement - mass of the disc before placement)/mass of the disc before placement × 100

(5)Reflow resistance

For an 80-pin flat package (QFP) with an external size of 20mm×14mm×2mm and equipped with a silicon chip of 8mm×10mm×0.4mm (lead frame material: copper alloy, the upper surface of the chip pad and the lead tip are silver-plated) , use the sealing epoxy resin molding material to perform molding under the above conditions, and perform post-hardening under the above conditions. The obtained package was humidified under conditions of 85°C and 85%RH for 168 hours. After that, reflow processing was performed at specified temperatures (250°C, 260°C, and 270°C) for 10 seconds each to visually observe the presence of cracks on the outside of the package and use an ultrasonic flaw detection device (Hitachi Construction Machinery Co., Ltd. Manufactured by HYE-FOCUS), observe whether peeling occurs inside the package. Reflow resistance was evaluated based on the total number of packages in which either cracking or peeling occurred relative to the number of test packages (10).

As shown in Tables 4 to 6, Examples 1 to 21 containing triazine compounds 1 to 10 corresponding to specific triazine compounds are compared with Comparative Examples 1 to 8 which do not contain a triazine compound. , improved adhesion to metal (silver), durable The weldability is also improved.

In Comparative Examples 9 and 10 containing triazine compound A and triazine compound B that are not equivalent to the specific triazine compound, compared with Comparative Examples 1 to 8 that do not contain a triazine compound, no reaction to the metal (silver) was observed. ), the bonding strength and reflow resistance are improved.

Claims (11)

A curable resin composition comprising: a curable resin; a hardener, the hardener being selected from the group consisting of aralkyl phenol resin, dicyclopentadiene phenol resin, triphenylmethane 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 novolak type phenol resin; and a compound represented by the following general formula (1);

[In the general formula (1), R ¹ to R ³ each independently represent a monovalent hydrocarbon group], and one or two of R ¹ to R ³ in the general formula (1) is 2,4-bis Methylphenyl. The curable resin composition as described in claim 1, 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 independently selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxygen groups, aromatic hydrocarbon oxygen groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic 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 ~5 integers]. The curable resin composition described in item 2 of the patent application, wherein at least one of R ⁴ to R ⁶ is a hydroxyl group. The curable resin composition as described in any one of items 1 to 3 of the patent application further includes an inorganic filler. The curable resin composition according to claim 1, wherein the curable resin includes epoxy resin. The curable resin composition as described in Item 5 of the patent application, wherein the epoxy resin includes a biphenyl-type epoxy resin, a stilbene-type epoxy resin. Grease, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymerized epoxy At least one of the group consisting of resin and aralkyl epoxy resin. The curable resin composition described in claim 1 of the patent application further includes a curing accelerator. The curable resin composition according to claim 7, wherein the curing accelerator contains a phosphonium compound. The curable resin composition as described in Item 7 or Item 8 of the patent application, wherein the hardening 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 with 1 to 18 carbon atoms, and two or more of R ¹ to R ³ can be bonded to each other to form a cyclic structure; 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 curable resin composition as described in claim 9, 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 ~ R ³ are each independently a hydrocarbon group with 1 to 18 carbon atoms, and two or more of R ¹ ~ R ³ can be bonded to each other to form a cyclic structure; R ⁴ ~ 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 includes: a component; and a cured product of the curable resin composition as described in any one of items 1 to 10 of the patent application for sealing the component.