TWI824034B - Curable resin composition and electronic component device - Google Patents

Abstract

A curable resin composition, comprising an epoxy resin and a curing agent, the curing agent comprising a phenol novolac resin that includes a structural unit derived from a phenol compound represented by the following Formula (1). In Formula (1), R¹ represents a hydrogen atom or a methyl group, R² represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

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 the 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. 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, for example, the use of silane coupling agents as a modifying material for inorganic fillers contained in sealing materials 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), etc. . [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

[Problem to be solved by the invention]

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 specific metals such as gold and silver is insufficient.

In view of the above circumstances, an object of the present invention is to provide a curable resin composition capable of obtaining a sealing structure with excellent adhesion to metal and reflow resistance, and an electronic component device obtained using the same. [Means to solve the problem]

Means for solving the above problems include the following embodiments. <1> A curable resin composition including an epoxy resin and a hardener including a phenol novolak resin containing a phenolic compound derived from a phenolic compound represented by the following general formula (1) structural unit.

[Chemical 1] (In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2) <2> Hardenability as described in <1> A resin composition in which the phenol novolak resin contains at least one structural unit derived from a phenolic compound represented by the following general formula (1-1) to general formula (1-3) as a component derived from the general formula ( 1) The structural unit of the represented phenolic compound.

[Chemicalization 2] (In the general formula (1-1) to the general formula (1-3), R ² has the same meaning as R ² in the general formula (1)) <3> Hardenability as described in <1> or <2> A resin composition wherein the phenol novolac resin further contains a structural unit derived from a phenolic compound other than the phenolic compound represented by the general formula (1). <4> The curable resin composition according to any one of <1> to <3>, wherein the hardener further contains a hardener other than the phenol novolac resin, and the phenol novolak resin contains a source. It is a structural unit of the phenolic compound represented by the general formula (1). <5> The curable resin composition according to any one of <1> to <4>, used as a sealing material for electronic component devices. <6> An electronic component device including: a component; and a cured product of the curable resin composition according to any one of <1> to <5> for sealing the component. [Effects of the invention]

According to the present invention, there are provided a curable resin composition capable of obtaining a sealing structure with excellent adhesion to metal and reflow resistance, and an electronic component device obtained using the same.

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 stated before and after "～" are included as the minimum value and the maximum value respectively. 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＞ The curable resin composition of the present disclosure includes an epoxy resin and a hardener including a phenol novolak resin (hereinafter, also referred to as Specific phenol novolak resin).

[Chemical 1]

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

The curable resin composition containing a specific phenol novolac resin has excellent adhesion to metal (especially gold) in a cured state. The reason for this is not necessarily clear, but it is thought that, for example, the aliphatic hydrocarbon group having 10 to 18 carbon atoms in the structural unit derived from the phenolic compound contained in the specific phenol novolac resin functions to improve the adhesion to the metal. Furthermore, it is thought that the aliphatic hydrocarbon group having 10 to 18 carbon atoms in the structural unit derived from the phenolic compound contained in the specific phenol novolac resin generates an elastic coefficient near the interface between the metal surface and the cured product of the curable resin composition. It works by reducing the water absorption rate, etc., and as a result, the reflow resistance is improved.

The curable resin composition containing a specific phenol novolac resin has excellent adhesion to metal in a cured state and is therefore suitable as a sealing material for a package including a lead frame in which at least the surface material is metal (especially gold). An example of a lead frame in which at least the surface is made of gold is a lead frame in which a copper lead frame called a pre-plated lead flame (PPF) is plated with Ni-Pd-Au.

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

[Chemical 1]

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

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

In a certain embodiment, the specific phenol novolak resin may contain at least a structural unit in which n is 1 (monohydric phenol), and a structural unit in which n is 2 (dihydric phenol) as derived from the general formula (1). The structural unit of the phenolic compound may include at least a structural unit in which n is 1 (monovalent phenol), and a structural unit in which the other hydroxyl group is in the meta position relative to one of the hydroxyl groups as the structural unit in which n is 2.

The specific phenol novolak resin may contain at least one structural unit derived from a phenol compound represented by the following general formula (1-1) to general formula (1-3) as the phenol derived from the general formula (1). The structural units of the compound may include all structural units derived from the phenolic compounds represented by General Formula (1-1) to General Formula (1-3).

[Chemicalization 2]

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

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

[Chemistry 5]

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

[Chemical 6]

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

In one embodiment, the specific phenol novolak resin may contain either or both of phenol and cresol as a structural unit derived from the phenol compound represented by the general formula (2), and may contain phenol and o- either or both of cresols.

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

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

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

The viscosity of a particular phenol novolac resin is not particularly limited. For example, the viscosity at 25°C is preferably 50 Pa·s or less, more preferably 30 Pa·s or less. The viscosity of a specific phenol novolac resin at 25°C is set to a point where an EHD-type rotational viscometer equipped with a conical rotor with a cone angle of 3° and a cone radius of 14 mm is rotated at 25°C for 1 minute, 10 times per minute (10 rpm) multiplied by the specified conversion factor (0.5) (Pa·s).

The hydroxyl equivalent weight of a specific phenol novolac resin is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 70 g/eq to 1000 g/eq is preferred, and 80 g/eq to 500 g/eq is more preferred.

The specific phenol novolak resin is preferably used in combination with a hardener other than the specific phenol novolak resin. That is, the curable resin composition preferably contains a specific phenol novolak resin and a hardener other than the specific phenol novolac resin as a hardener.

When the curable resin composition contains a specific phenol novolac resin and a hardener other than the specific phenol novolak resin as a hardener, from the perspective of curability, the specific phenol novolac resin accounts for The proportion of is preferably 50% or less on an equivalent basis, more preferably 30% or less, and further preferably 20% or less. From the viewpoint of improving the adhesion to metal, the proportion of the specific phenol novolac resin in the entire hardener is preferably 1% or more on an equivalent basis, more preferably 3% or more, and still more preferably 5% or more.

The type of curing agent other than the specific phenol novolak resin is not particularly limited and can be selected in accordance with the desired characteristics of the curable resin composition. Specific examples of the hardener will be described later.

(epoxy resin) The type of epoxy resin contained in the curable resin composition is not particularly limited, and can be selected according to the desired characteristics of the curable resin composition. Specific examples of the epoxy resin include phenol compounds selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and α-naphthol, β - Novolak resin is obtained by condensation or co-condensation of at least one phenolic compound in the group consisting of naphthol compounds such as naphthol and dihydroxynaphthalene and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde under an acidic catalyst and a novolak-type epoxy resin (phenol novolak-type epoxy resin, o-cresol novolak-type epoxy resin, etc.) obtained by epoxidizing the novolak resin; making the phenolic compound, benzaldehyde, and water Triphenylmethane-type epoxy resin is obtained by condensing or co-condensing aromatic aldehyde compounds such as maleic aldehyde under an acidic catalyst to obtain triphenylmethane-type phenol resin, and then epoxidizing the triphenylmethane-type phenol resin; A copolymerized epoxy resin obtained by co-condensing the phenolic compound, naphthol compound and aldehyde compound under an acidic catalyst to obtain a novolak resin and epoxidizing the novolak resin; as bisphenol A, bisphenol Diphenylmethane-type epoxy resins as diglycidyl ethers such as F; biphenyl-type epoxy resins as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-based phenols Stilrene-type epoxy resins that are diglycidyl ethers of compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers of bisphenol S, etc.; 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, epoxy resins such as silicone resin epoxides and acrylic resin epoxides can also be cited. 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 "specified 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.

[Chemical 8]

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 and represents 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 is a hydrogen atom, such as 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 and represents 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 substitution position of the oxygen atom in R ¹² 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.

[Chemical 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 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.

[Chemical 11]

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 and represents 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 a product 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.

[Chemical 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 may be the same or different. i each independently represents an integer from 0 to 3. n is the average value and represents 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 each independently represents an integer from 0 to 3. n is the average value and represents 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.) in which i is 0 and k is 0, etc. It is available as a commercial product.

[Chemical 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. i each independently represents an integer from 0 to 3, and k each independently represents an integer from 0 to 4. n is the average value and represents 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 preferred, and an epoxy resin represented by the following general formula (IX) is more preferred. 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.

[Chemical 15]

In formula (IX), R ¹⁹ to R ²¹ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i each independently represents an integer from 0 to 3, j each independently represents an integer from 0 to 2, and k each independently represents an integer from 0 to 4. l and m are respectively average values and are numbers 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 to R ²¹ are the same as the definitions of i, j and k in R ¹⁹ to R ²¹ in formula (IX). same. n is 1 (when bonded via a methylene group) or 0 (when not bonded through a methylene group).

[Chemical 16]

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

[Chemical 17]

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 its derivatives, 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), i is 0 and R ³⁸ is a hydrogen atom, NC-3000S (trade name of Nippon Kayaku Co., Ltd.), i is 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.), in which i is 0, j is 0, and k is 0, is commercially available as Obtained by product.

[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 may be the same or different. i is each independently an integer from 0 to 3, j is each independently an integer from 0 to 2, k is each independently an integer from 0 to 4, and l is each independently an integer from 0 to 6. n is an 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 “may be the same or different” refers to, for example, 8 to R in the general 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, and the viscosity of the curable resin composition during melt molding will be reduced, thereby suppressing the occurrence of filling defects and deformation of bonding wires (metal wires that connect components and leads). tendency. More preferably, n is set in the range of 0 to 4.

The epoxy equivalent weight of the epoxy resin is not particularly limited. From the viewpoint of balancing various characteristics such as formability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq.

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

From the viewpoint of strength, fluidity, heat resistance, formability, etc., the content of the epoxy resin in the curable resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass. %.

(Hardening agents other than specific phenol novolac resins) The type of hardener other than the specific phenol novolac resin contained in the curable resin composition is not particularly limited, and can be selected according to the type of epoxy resin used together, the desired characteristics of the curable resin composition, etc. . Examples of hardeners used together with epoxy resins include phenol hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, and block isocyanate hardeners. 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. , resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenolic 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-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; combining the phenolic compound with benzaldehyde, salicylic aldehyde and other aromatic compounds triphenylmethane type phenol resin obtained by condensation or co-condensation of aldehyde compounds 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 a combination 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.

[Chemical 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 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 each independently an integer from 0 to 3, j is each independently an integer from 0 to 2, k is each independently an integer from 0 to 4, and p is each independently an integer from 0 to 4. n is an 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.

[Chemistry 20]

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

[Chemistry 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 each independently an integer from 0 to 3, and k is each independently an integer from 0 to 4. 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 of Air Water Chemical Co., Ltd.) in which i is 0, k is 0, and q is 0 is commercially available as Obtained by product.

[Chemistry 22]

In formula (XVII), R ³² to R ³⁴ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is each independently an integer from 0 to 3, k is each independently an integer from 0 to 4, and q is each independently 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.

[Chemistry 23]

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 each independently represents an integer from 0 to 3. n is the average value and represents a number from 0 to 10.

The words “may be 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 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 , the respective numbers included in the formula may be the same or different. In addition, R ²² to R ³⁶ may each 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.

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. The average n per 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 phenolic hardener) is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 70 g/eq to 1000 g/eq is preferred, and 80 g/eq to 500 g/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, the temperature is preferably 40°C to 180°C, and from the viewpoint of workability during production of the curable resin composition, the temperature is more preferably 50°C to 130°C.

The equivalent ratio of the epoxy resin and the hardener, that is, the ratio of the number of functional groups in the hardener to the number of functional groups in the epoxy resin (number of functional groups in the hardener/number of functional groups in the epoxy 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, tris(alkyl·alkoxy)phosphine phenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(tris(trialkylphenyl)phosphine Tertiary phosphines such as alkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; maleic anhydride, 1,4- Benzoquinone, 2,5-toluoquinone, 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 π bonds such as diazophenylmethane The compound with intramolecular polarization formed; by 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-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 by reacting halogenated phenol compounds such as bromo-2-naphthol and 4-bromo-4'-hydroxybiphenyl through dehydrohalogenation; tetraphenylphosphonium and other four-substituted phosphonium, Tetra-p-toluene borate and other tetra-substituted phosphoniums and tetra-substituted borates that do not have a phenyl group bonded to the boron atom; salts of tetra-substituted phosphonium and anions derived from phenolic compounds after removing protons, tetra-substituted phosphonium and auto-carboxylic acid compounds Salts of anions after removing protons, 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 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 cyclic 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 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 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 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 the substituent include alkoxy groups such as methoxy, ethoxy, butoxy, and tert-butoxy groups, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amino groups, halogen atoms, and the like. 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 even 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, cycloalkenyl groups such as cyclopentenyl and cyclohexenyl, and the like. 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, amine 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 having 6 to 12 carbon atoms or a substituent-containing aryl group having 6 to 12 carbon atoms is preferred, and an unsubstituted aryl group having 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 in this case 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) means a fatty acid containing 1 to 18 carbon atoms, which 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, phenoxycarbonyl group, and methyl group. Aromatic hydrocarbonoxycarbonyl groups such as phenoxycarbonyl group, these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, halogen atoms, etc. Key et al.

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 may be bonded to each other to form a cyclic structure" as R ⁴ to R ⁷ in the general formula (I-1) means 2 to 4 R ⁴ to R ⁷ bonds, and 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 preferred 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).

[Chemical 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 cyclic 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 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, and the like. 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 (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.

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

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 these, fused silica is preferable from the viewpoint of reduction in linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. 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 to 90 volume% of the entire curable resin composition, more preferably 35 to 80 volume%, and still more preferably 40 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 size of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 10 μm, more preferably 0.5 μm to 5 μm. 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 ability into 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, the inorganic filler is extracted from a self-curing resin composition or cured product using an organic solvent, nitric acid, aqua regia, etc., and is fully dispersed using an ultrasonic disperser to prepare a dispersion. 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 a 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}

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 octacarboxylic acid and stearic acid, higher fatty acid metal salts, ester waxes such as octacarboxylic acid 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 relative to 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 mentioned: after fully mixing the predetermined compounding amount of components with a mixer etc., melt-kneading with a grinding roll, an extruder etc., cooling and grinding|pulverizing. 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 is 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 devices＞ 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 chips, 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 (TSOP), Thin Quad Flat Package, TQFP) and other general resin-sealed ICs, which have a component that is fixed to a lead frame and the terminal portion and lead portion of components such as bonding pads are connected by wire bonding, bumps, etc., and then a curable resin composition is used and A structure for sealing such as transfer molding; Tape Carrier Package (TCP), which has a structure that uses a curable resin composition to seal components connected to a carrier tape with bumps; Chip On Board (Chip On Board) , COB) modules, hybrid ICs, polycrystalline modules, etc., which have the function of using a curable resin composition to seal components on wiring formed by wire bonding, flip chip bonding, solder, etc. Structure; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which have a surface on which a support member for wiring board connection terminals is formed on the back surface A structure in which components are mounted on the support member and connected to wiring formed on the supporting 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 Table 1 and Table 2, and roller kneading was performed at a kneading temperature of 80° C. and a kneading time of 15 minutes to prepare Examples 1 to 2. 15. The curable resin compositions of Comparative Examples 1 to 8.

(epoxy resin) ·Epoxy resin 1: biphenyl-type epoxy resin with an epoxy equivalent of 196 g/eq 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 g/eq and a softening point of 59°C (Nippon Steel & Sumitomo Metal 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 g/eq and a softening point of 58°C (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 g/eq and a softening point of 56°C (Nippon Kayaku Co., Ltd., trade name "NC-3000")

(Hardening agent of comparative example) Hardener A: Phenol aralkyl resin with a hydroxyl equivalent of 176 g/eq and a softening point of 70°C (Meiwa Chemical Co., Ltd., trade name "MEH-7800") Hardener B: Biphenyl skeleton type phenol aralkyl resin with a hydroxyl equivalent of 199 g/eq and a softening point of 89°C (Meiwa Kasei Co., Ltd., trade name "MEH-7851")

(Hardening agent of Examples) Specific phenol novolac resin 1: a mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A) using formaldehyde, That is, a novolac resin with a hydroxyl equivalent of 223 g/eq and a viscosity of 19.3 Pa·s at 25°C obtained by condensation polymerization of industrial cashew nut shell liquid and phenol (Kunyoung Chemical Industry Co., Ltd., product Name "ELP83H") Specific phenol novolak resin 2: a mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A) using formaldehyde, that is, industrial Novolac resin with a hydroxyl equivalent of 209 g/eq and a viscosity of 14.0 Pa·s at 25°C obtained by condensation polymerization of cashew nut shell liquid, cresol and phenol (Kunyoung Chemical Industry Co., Ltd., trade name "ELPC80") Specific phenol novolak resin 3: a mixture of general formula (1-1) to general formula (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A) using formaldehyde, that is, industrial cashew nut shell liquid, Specific phenol novolac resin (Kunei Chemical Industry Co., Ltd., trade name "ELPC75"), which is a novolac resin with a hydroxyl equivalent of 204 g/eq and a viscosity of 23.6 Pa·s at 25°C, obtained by condensation of cresol and phenol. 4: A mixture of general formulas (1-1) to (1-3) in which R ² is an aliphatic hydrocarbon group represented by group (A), that is, industrial cashew nut shell liquid and cresol, is condensed with formaldehyde. The resulting novolak resin has a hydroxyl equivalent of 204 g/eq and a viscosity of 20.2 Pa·s at 25°C (Qunyoung Chemical Industry Co., Ltd., trade name "ELC75")

(Harding accelerator) Hardening accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler) spherical fused silica (volume average particle diameter 17.5 μm, specific surface area 3.8 m ² / g) (Coupling agent) Epoxysilane (γ-glycidoxypropyltrimethoxysilane) (Coloring agent) Carbon black (Mitsubishi Chemical Co., Ltd., trade name "MA-100") (Release agent) Palm Wax (Cera NODA Co., Ltd.)

[Table 1] Project Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Allocation table Epoxy resin 1 100 2 100 100 100 100 100 100 100 100 100 100 100 100 3 100 4 100 Hardener A 76.3 53.0 59.8 56.2 59.3 60.5 43.7 53.0 53.0 53.0 53.0 53.0 53.0 B 60.0 60.0 1 17.1 11.9 11.9 11.9 13.4 7.9 4.0 2.4 23.7 11.9 11.9 11.9 2 11.1 3 10.9 4 10.9 Coupling agent 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 hardening accelerator 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 palm wax 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 carbon black 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 fused silica 1682 1452 1508 1508 1519 1445 1439 1435 1472 1017 1201 1814 1445 1443 1443 Amount of molten silica (mass %) 89 89 89 89 89 89 89 89 89 85 87 91 89 89 89

[Evaluation of curable resin composition] The characteristics of the curable resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 8 were evaluated by the following characteristic tests. The evaluation results are shown in Table 3 and Table 4. In addition, unless otherwise specified, the curable resin composition 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 in compliance with EMMI-1-66, the curable resin composition was molded under the conditions described above, and the flow distance (cm) was determined.

(2) Hardness when hot The curable resin composition was formed into a circular plate with a diameter of 50 mm and a thickness of 3 mm under the above conditions. Immediately after forming, a Shore D-type hardness tester (Uejima Manufacturing Co., Ltd., HD-1120 (D type)) was used. Make a determination.

(3) Shear bonding strength at 260℃ Under the above conditions, a curable resin composition was formed on a copper alloy plate (Pd-PPF) with a bottom surface diameter of 4 mm, an upper surface diameter of 3 mm, and a height of 4 mm, and post-hardening was performed under the above conditions. After that, a bondtester (Bondtester) (Dage Japan Co., Ltd., Series 4000) was used to maintain the temperature of the copper plate at 260°C and to determine the shear bonding force at a shear speed of 50 μm/s ( MPa).

(4) Water absorption rate The circular plate formed in (2) is post-hardened under the above conditions. Thereafter, the obtained disc was left for 168 hours under conditions of 85° C. and 60% RH, and the mass change before and after being left 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 20 mm × 14 mm × 2 mm (lead frame material: copper alloy plate (Pd-PPF)) equipped with a silicon chip of 8 mm × 10 mm × 0.4 mm, using hardening The flexible resin composition is molded under the above conditions and post-hardened under the above conditions. The obtained package was humidified under conditions of 85°C and 60% RH for 168 hours. After that, reflow processing was performed at specified temperatures (250°C, 260°C, and 270°C) for 10 seconds, and the presence or absence of cracks on the outside of the package was visually observed and an ultrasonic flaw detection device (Hitachi Construction Machinery Co., Ltd. Manufacturing, 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).

[table 3] Project Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Evaluation items Swirl (cm) 145 125 108 116 119 123 120 118 132 146 135 115 128 122 121 Hot hardness 76 73 71 71 73 76 78 79 71 70 71 76 73 74 74 260℃ shear bonding force 0.48 0.49 0.47 0.45 0.43 0.39 0.35 0.29 0.53 0.45 0.47 0.51 0.51 0.45 0.47 Water absorption rate (%) 0.23 0.19 0.18 0.16 0.19 0.19 0.17 0.18 0.17 0.23 0.20 0.16 0.18 0.20 0.19 Reflow resistance (250℃) 0/10 0/10 0/10 0/10 0/10 0/10 0/10 6/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 Reflow resistance (260℃) 7/10 0/10 2/10 3/10 4/10 5/10 9/10 10/10 0/10 5/10 2/10 0/10 0/10 1/10 0/10 Reflow resistance (270℃) 10/10 3/10 8/10 7/10 9/10 10/10 10/10 10/10 0/10 10/10 6/10 0/10 2/10 7/10 6/10

[Table 4] Project Comparative example 1 2 3 4 5 6 7 8 Evaluation items Swirl (cm) 135 117 102 109 108 140 129 108 Hot hardness 81 79 77 77 78 76 77 80 260℃ shear bonding force 0.22 0.24 0.21 0.23 0.25 0.19 0.22 0.26 Water absorption rate (%) 0.24 0.19 0.19 0.18 0.21 0.24 0.22 0.17 Reflow resistance (250℃) 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 Reflow resistance (260℃) 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 Reflow resistance (270℃) 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10

As shown in Tables 3 and 4, Examples 1 to 15 containing specific phenol novolac resin 1 to 4 are compared with Comparative Examples 1 to 8 containing no specific phenol novolac resin. The adhesion to metal (Pd-PPF) is improved, and the reflow resistance is also improved.

without

without

Claims (6)

A hardening resin composition, comprising an epoxy resin and a hardener, the hardening agent comprising a phenol novolak resin, the phenol novolak resin containing a structural unit derived from cashew nut shell liquid, the hardening resin composition at 25 It is solid at ℃ and atmospheric pressure. The curable resin composition described in item 1 of the patent application, wherein the hydroxyl equivalent of the phenol novolac resin is 70g/eq~223g/eq. The curable resin composition described in claim 1, wherein the phenol novolac resin further contains structural units derived from phenolic compounds other than cashew nut shell liquid. The curable resin composition as described in any one of items 1 to 3 of the patent application, wherein the hardener further includes a hardener other than the phenol novolac resin, and the phenol novolak resin contains a source Structural unit from cashew nut shell liquid. The curable resin composition described in any one of items 1 to 3 of the patent application is used as a sealing material for electronic component devices. 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 5 of the patent application for sealing the component.