CN112805315A

CN112805315A - Curable resin composition and electronic component device

Info

Publication number: CN112805315A
Application number: CN201980064930.4A
Authority: CN
Inventors: 中村真也
Original assignee: Showa Denko KK
Current assignee: Resonac Holdings Corp
Priority date: 2018-10-18
Filing date: 2019-10-15
Publication date: 2021-05-14
Also published as: JP2020063388A; WO2020080370A1; TW202028346A; JP7484081B2; TWI824034B

Abstract

A curable resin composition comprising an epoxy resin and a curing agent, wherein the curing agent comprises a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1). In the general formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

Description

Curable resin composition and electronic component device

Technical Field

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

Background

With recent miniaturization, weight reduction, high performance, and the like of electronic devices, higher density mounting has been advanced. Accordingly, the mainstream of the electronic component device is changed from the conventional pin insertion type package to the surface mounting type package such as an Integrated Circuit (IC) or a Large Scale Integrated Circuit (LSI).

The surface mount type package is mounted in a different method from the conventional pin insertion type package. That is, when mounting the pins to the wiring board, the conventional pin insertion type package is soldered from the back surface of the wiring board after inserting the pins into the wiring board, and therefore the package is not directly exposed to high temperature. However, in the surface mounting type package, since the entire electronic component device is processed by a solder bath, a reflow device, or the like, the package is directly exposed to a soldering temperature (reflow temperature). As a result, when the package absorbs moisture, moisture rapidly expands due to moisture absorption at the time of soldering, and the generated vapor pressure acts as a peeling stress, so that peeling occurs between an interposer such as an element or a lead frame and the sealing material, which may cause a package crack, a failure in electrical characteristics, or the like. Therefore, development of a sealing material having excellent adhesion to an insert and further excellent solder heat resistance (reflow resistance) has been desired.

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

[ Prior art documents ]

[ patent document ]

Patent document 1: japanese patent laid-open No. Hei 11-147939

Patent document 2: japanese patent laid-open No. 2000-103940

Disclosure of Invention

[ problems to be solved by the invention ]

However, in the method using an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent, the effect of improving the adhesion of the surface of the lead frame to the metal may be insufficient. Further, when a silane coupling agent containing a sulfur atom is used, there is a problem that the effect of improving the adhesion to a specific metal such as gold or silver is insufficient.

In view of the above circumstances, an object of the present invention is to provide a curable resin composition that can provide a sealing structure having excellent adhesion to metal and reflow resistance, and an electronic component device obtained using the same.

[ means for solving problems ]

Means for solving the problems include the following embodiments.

<1> a curable resin composition comprising an epoxy resin and a curing agent, wherein the curing agent comprises a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1).

[ solution 1]

(in the general formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2)

<2> the curable resin composition according to <1>, wherein the phenol novolac resin contains at least one of structural units derived from phenol compounds represented by the following general formulae (1-1) to (1-3) as a structural unit derived from phenol compounds represented by the general formula (1).

[ solution 2]

In (general formula (1-1) to (1-3), R²And R in the general formula (1)²To the same extent)

<3> the curable resin composition according to <1> or <2>, wherein the phenol novolac resin further comprises a structural unit derived from a phenol compound other than the phenol compound represented by the general formula (1).

<4> the curable resin composition according to any one of <1> to <3>, wherein the curing agent further comprises a curing agent other than a phenol novolac resin containing a structural unit derived from the phenol compound represented by the general formula (1).

<5> the curable resin composition according to any one of <1> to <4>, which is used as a sealing material for electronic component devices.

<6> an electronic part device comprising: an element; and a cured product of the curable resin composition according to any one of <1> to <5> sealing the element.

[ Effect of the invention ]

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

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps) are not necessarily required unless otherwise explicitly indicated. The same is true for numerical values and ranges thereof, and the invention is not limited thereto.

In the present disclosure, the term "step" includes a step other than a step independent from other steps, as long as the purpose of the step is achieved, even when the step cannot be clearly distinguished from other steps.

In the present disclosure, numerical values before and after the "to" are included in the numerical range indicated by the "to" are used as the minimum value and the maximum value, respectively.

In the numerical ranges recited in the present disclosure, the upper limit or the lower limit recited in one numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.

In the present disclosure, the content or content of each component in the composition refers to the total content or content of a plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.

In the present disclosure, the particle diameter of each component in the composition indicates a value for a mixture of a plurality of types of particles present in the composition, unless otherwise specified, when a plurality of types of particles corresponding to each component are present in the composition.

< curable resin composition >

The curable resin composition of the present disclosure includes an epoxy resin and a curing agent including a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1) (hereinafter, also referred to as a specific phenol novolac resin).

[ solution 1]

In the formula, R¹Represents a hydrogen atom or a methyl group, R²Represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

A curable resin composition containing a specific phenol novolac resin is excellent in adhesion to a metal (particularly gold) in a cured state. The reason for this is not necessarily clear, but it is considered that, for example, an aliphatic hydrocarbon group having 10 to 18 carbon atoms contained in a structural unit derived from a phenol compound contained in a specific phenol novolac resin acts to improve adhesion to a metal. Further, it is considered that the aliphatic hydrocarbon group having 10 to 18 carbon atoms included in the structural unit derived from a phenol compound contained in the specific phenol novolac resin acts to reduce the elastic coefficient, the water absorption rate, and the like in the vicinity of the interface between the metal surface and the cured product of the curable resin composition, and as a result, reflow resistance is improved.

Since a curable resin composition containing a specific phenol novolac resin has excellent adhesion to a metal in a cured state, it is preferable as a sealing material for a package including a lead frame of which at least the surface is made of a metal (particularly, gold). As a Lead frame whose material of at least the surface is gold, for example, a Lead frame obtained by Plating a copper Lead frame called a Pre-plated Lead frame (PPF) with Ni — Pd — Au is cited.

(specific phenol novolak resin)

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

[ solution 2]

In the general formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents 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 phenol 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 novolac resin contains two or more structural units derived from the phenol compound represented by the general formula (1), the arrangement thereof is not particularly limited, and may be arranged regularly or irregularly.

In one embodiment, the specific phenol novolac 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 structural units derived from the phenol compound represented by the general formula (1), or may contain at least a structural unit in which n is 1 (monohydric phenol) and a structural unit in which one of the hydroxyl groups is meta to the other hydroxyl group as the structural unit in which n is 2.

The specific phenol novolac resin may contain at least one of the structural units derived from the phenol compounds represented by the following general formulae (1-1) to (1-3) as the structural unit derived from the phenol compound represented by the general formula (1), or may contain all of the structural units derived from the phenol compounds represented by the general formulae (1-1) to (1-3).

[ solution 4]

In the general formulae (1-1) to (1-3), R²And R in the general formula (1)²Are the same meaning.

In the general formula (1), R²The C10-18 aliphatic hydrocarbon group may be a C13-16 aliphatic hydrocarbon group, and may or may not have an unsaturated double bond. At R²When the aliphatic hydrocarbon group having 10 to 18 carbon atoms has an unsaturated double bond, the number thereof is not particularly limited, and may be, for example, 1 to 5. R²The aliphatic hydrocarbon group having 10 to 18 carbon atoms may be branched or unbranched, but is preferably unbranched. As R²Specific examples of the aliphatic hydrocarbon group having 10 to 18 carbon atoms include aliphatic hydrocarbon groups represented by the following group (a) (where x represents a bonding position with an aromatic ring). R in specific phenol novolac resins²The structures of the aliphatic hydrocarbon groups having 10 to 18 carbon atoms may be the same or different.

[ solution 6]

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

[ solution 5]

In the general formula (2), R¹Represents a hydrogen atom or a methyl group, 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 novolac 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), or may contain either or both of phenol and o-cresol.

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

The method of synthesizing the specific phenol novolac 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 novolac 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 20000.

The viscosity of the specific phenol novolac resin is not particularly limited. For example, the viscosity at 25 ℃ is preferably 50 pas or less, more preferably 30 pas or less. The viscosity of the specific phenol novolak resin at 25 ℃ was set to a value (Pa · s) obtained by multiplying a measurement value obtained by rotating an EHD type rotational viscometer equipped with a cone having a cone angle of 3 ° and a cone radius of 14mm at 25 ℃ for 1 minute and 10 times per minute (10rpm) by a predetermined conversion coefficient (0.5).

The hydroxyl equivalent weight of the specific phenol novolac resin is not particularly limited. From the viewpoint of balance among various properties such as moldability, reflow resistance and electrical reliability, it is preferably from 70 to 1000g/eq, more preferably from 80 to 500 g/eq.

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

When the curable resin composition contains the specific phenol novolac resin and a curing agent other than the specific phenol novolac resin as the curing agent, the proportion of the specific phenol novolac resin in the entire curing agent is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less on an equivalent basis from the viewpoint of curing properties. From the viewpoint of improving the adhesion to metals, the proportion of the specific phenol novolac resin in the entire hardener is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more on an equivalent basis.

The type of the curing agent other than the specific phenol novolac resin is not particularly limited, and may be selected according to desired characteristics of the curable resin composition. Specific examples of the curing agent will be described later.

(epoxy resin)

The type of the epoxy resin contained in the curable resin composition is not particularly limited, and may be selected according to desired characteristics of the curable resin composition, and the like. Specific examples of the epoxy resin include: a novolak-type epoxy resin (e.g., a phenol novolak-type epoxy resin, an o-cresol novolak-type epoxy resin, etc.) obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, and bisphenol F, and naphthol compounds such as α -naphthol, β -naphthol, and dihydroxynaphthalene, with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolak resin, and epoxidizing the novolak resin; a triphenylmethane type epoxy resin obtained by subjecting the phenolic compound and an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde to condensation or co-condensation in the presence of an acidic catalyst to obtain a triphenylmethane type phenol resin and epoxidizing the triphenylmethane type phenol resin; a co-polymerization type epoxy resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound in the presence of an acidic catalyst to obtain a novolac resin and epoxidizing the novolac resin; diphenylmethane-type epoxy resins as diglycidyl ethers of bisphenol a, bisphenol F, and the like; biphenyl type epoxy resins as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; a stilbene type epoxy resin as a diglycidyl ether of a stilbene (stilbene) type phenol compound; an epoxy resin containing a sulfur atom as a diglycidyl ether of bisphenol S or the like; epoxy resins as glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins as glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl amine type epoxy resins obtained by replacing active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, and isocyanuric acid with a glycidyl group; a dicyclopentadiene type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; alicyclic epoxy resins such as vinylcyclohexene dioxide diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, and 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-m-dioxane obtained by epoxidizing an olefin bond in the molecule; a p-xylene-modified epoxy resin as a glycidyl ether of the p-xylene-modified phenol resin; a m-xylene-modified epoxy resin which is a glycidyl ether of a m-xylene-modified phenol resin; terpene-modified epoxy resins as glycidyl ethers of terpene-modified phenol resins; a dicyclopentadiene-modified epoxy resin which is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin which is a glycidyl ether of a cyclopentadiene-modified phenol resin; a polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of the polycyclic aromatic ring-modified phenol resin; naphthalene type epoxy resins as glycidyl ethers of phenol resins containing naphthalene rings; a halogenated phenol novolac type epoxy resin; p-phenylene bisphenol type epoxy resin; trimethylolpropane type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing an olefin bond with a peracid such as peracetic acid; aralkyl type epoxy resins obtained by epoxidizing aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins. Further, epoxy resins such as epoxy of silicone resin and epoxy of acrylic resin may be mentioned. These epoxy resins may be used alone or in combination of two or more.

Among the above epoxy resins, from the viewpoint of balance between reflow resistance and fluidity, epoxy resins selected from the group consisting of biphenyl type epoxy resins, diphenylethylene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing type epoxy resins, novolak type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, copolymerized type epoxy resins, and aralkyl type epoxy resins (these are referred to as "specific epoxy resins") are preferable. The specific epoxy resin may be used alone or in combination of two or more.

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

Among the specific epoxy resins, a biphenyl type epoxy resin, a diphenylethylene type epoxy resin, a diphenylmethane type epoxy resin or a sulfur atom containing type epoxy resin is more preferable from the viewpoint of fluidity, and a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin or an aralkyl type epoxy resin is preferable from the viewpoint of heat resistance. 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 preferable. In the epoxy resin represented by the following general formula (II), R⁸The 3, 3 ', 5, 5 ' positions of the 4-and 4 ' -positions of the oxygen atom are methyl and the other R is⁸YX-4000H (trade name, Mitsubishi chemical corporation) which is a hydrogen atom, all of R⁸4, 4' -bis (2, 3-epoxypropoxy) biphenyl being a hydrogen atom, all R⁸In the case of a hydrogen atom and R⁸Substituted by middle oxygen atomsWhen the positions of (A) are 4-position and 4 ' -position, the 3, 3 ', 5, 5 ' -position is methyl and the other R is⁸A mixed product in the case of a hydrogen atom, i.e., YL-6121H (trade name) or the like is available as a commercially available product.

[ solution 8]

In the formula (II), R⁸Each of which represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number of 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 preferable. In the epoxy resin represented by the following general formula (III), R⁹The 3, 3 ', 5, 5 ' positions of the 4-and 4 ' -positions of the oxygen atom are methyl and the other R is⁹Is a hydrogen atom, R¹⁰All are hydrogen atoms, and R⁹In which 3 of the 3, 3 ', 5, 5' positions are methyl and 1 is tert-butyl and R is other than this⁹Is a hydrogen atom, R¹⁰ESLV-210 (trade name, Sumitomo chemical Co., Ltd.) or the like, which is a mixture of all hydrogen atoms, is available as a commercially available product.

[ solution 9]

In the formula (III), R⁹And R¹⁰The monovalent organic groups may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. n is an average value and represents a number of 0 to 10.

The diphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. In the epoxy resin represented by the following general formula (IV), R¹¹Are each a hydrogen atom, R¹²The 3, 3 ', 5, 5 ' positions of the 4-and 4 ' -positions of the oxygen atom are methyl and the other R is¹²YSLV-80XY (trade name, Nissian iron goddess chemical Co., Ltd.) or the like, which is a hydrogen atom, is available as a commercially available product.

[ solution 10]

In the formula (IV), R¹¹And R¹²The monovalent organic groups may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. n is an average value and represents a number of 0 to 10.

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. Examples of the epoxy resin include epoxy resins represented by the following general formula (V). In the epoxy resin represented by the following general formula (V), R¹³When the positions substituted by the oxygen atom are 4-position and 4 ' -position, the 3, 3 ' -position is t-butyl, the 6, 6 ' -position is methyl and the other R is¹³YSLV-120TE (trade name, Nippon iron-god chemical Co., Ltd.) or the like, which is a hydrogen atom, is available as a commercially available product.

[ solution 11]

In the formula (V), R¹³The monovalent organic groups may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. n is an average value and represents a number of 0 to 10.

The novolac-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac-type phenol resin. For example, epoxy resins obtained by epoxidizing novolak phenol resins such as phenol novolak resins, cresol novolak resins, and naphthol novolak resins by a method such as glycidyl etherification are preferable, and epoxy resins represented by the following general formula (VI) are more preferable. In the followingIn the epoxy resin represented by the general formula (VI), R¹⁴All being hydrogen atoms, R¹⁵ESCN-190, ESCN-195 (sumitomo chemical corporation, trade name) which is methyl, i ═ 1; r¹⁴N-770, N-775 (trade name, dear-son (DIC) gmbh) all of which is a hydrogen atom, i ═ 0; having R¹⁴Moieties wherein all are hydrogen atoms, i-0, with i-1, R¹⁵is-CH (CH)₃) -a styrene-modified phenol novolac type epoxy resin of Ph part, namely, YDAN-1000-10C (trade name, product name, yokuwa chemical corporation); having R¹⁴All being hydrogen atoms, i ═ 1, R¹⁵Moieties being methyl with i ═ 2, R¹⁵A benzyl-modified cresol novolak type epoxy resin in which one is a methyl group and one is a benzyl group, that is, HP-5600 (trade name, dear-son (DIC) corporation), and the like are available as commercially available products.

[ solution 12]

In the formula (VI), R¹⁴The monovalent organic groups may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. R¹⁵The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i independently represent an integer of 0 to 3. n is an average value and represents a number of 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 preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (trade name, Dean (DIC) corporation) having i ═ 0 is available as a commercially available product.

[ solution 13]

In the formula (VII), R¹⁶The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i independently represent an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

The triphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin obtained by using a compound having a triphenylmethane skeleton as a raw material. For example, epoxy resins obtained by glycidyletherifying a triphenylmethane-type phenol resin such as a novolak-type phenol resin containing a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group are preferable, and epoxy resins represented by the following general formula (VIII) are more preferable. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (trade name, Mitsubishi chemical corporation), EPPN-502H (trade name, Nippon chemical corporation) and the like, in which i is 0 and k is 0, are available as commercially available products.

[ solution 14]

In the formula (VIII), R¹⁷And R¹⁸The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i independently represent an integer of 0 to 3, and k independently represent an integer of 0 to 4. n is an average value and represents a number of 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 is not particularly limited as long as it is an epoxy resin obtained from a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, the epoxy resin is preferably obtained by glycidyl etherification of a novolac-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton, and more preferably an epoxy resin represented by the following general formula (IX). In the epoxy resin represented by the following general formula (IX), R²¹NC-7300 (trade name, Nippon chemical Co., Ltd.) or the like, which is a methyl group, i is 1, j is 0, and k is 0, is available as a commercially available product.

[ solution 15]

In the formula (IX), R¹⁹～R²¹The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i independently represents an integer of 0 to 3, j independently represents an integer of 0 to 2, and k independently represents an integer of 0 to 4. l and m are each an average value and are a number of 0 to 10, and (l + m) represents a number of 0 to 10. The epoxy resin represented by the formula (IX) has a terminal of either the following formula (IX-1) or formula (IX-2). In the formulae (IX-1) and (IX-2), R¹⁹～R²¹The definitions of i, j and k in (A) and R in formula (IX)¹⁹～R²¹I, j and k in (1) are as defined. n is 1 (in the case of bonding via methylene) or 0 (in the case of bonding without methylene).

[ solution 16]

Examples of the epoxy resin represented by the general formula (IX) include: a random copolymer randomly including 1 constituent unit and m constituent units, an alternating copolymer alternately including 1 constituent unit and m constituent units, a copolymer regularly including 1 constituent unit and m constituent units, a block copolymer including 1 constituent unit and m constituent units in a block form, and the like. Any of these may be used alone, or two or more of these may be used in combination.

As the co-polymerization type epoxy resin, a methoxy naphthalene-cresol formaldehyde co-condensation type epoxy resin containing the following 2 kinds of structural units in a random, alternate or block order, that is, Eibolon (EPICLON) HP-5000 (trade name, Diegon (DIC) Co., Ltd.) represented by the following general formula is also preferable. In the general formula, n and m are average values and are numbers of 0 to 10, respectively, (n + m) represents numbers of 0 to 10, preferably n and m are average values and are numbers of 1 to 9, respectively, and (n + m) represents numbers of 2 to 10.

[ solution 12]

The aralkyl type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by using, as a raw material, at least one selected from the group consisting of phenol compounds such as phenol and cresol, naphthol compounds such as naphthol and dimethylnaphthol, and a phenol resin synthesized from dimethoxyp-xylene, bis (methoxymethyl) biphenyl, or a derivative thereof. For example, the epoxy resin is preferably obtained by glycidyletherifying a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyp-xylene, bis (methoxymethyl) biphenyl or derivatives thereof, and more preferably the epoxy resins represented by the following general formula (X) and general formula (XI).

In the epoxy resin represented by the following general formula (X), i is 0 and R³⁸NC-3000S (trade name, Nippon chemical Co., Ltd.) as a hydrogen atom in a mass ratio of 80: 20 with i being 0 and R being³⁸Epoxy resins being hydrogen atoms with all R of the formula (II)⁸CER-3000 (trade name, manufactured by Nippon chemical Co., Ltd.) and the like, which is a mixture of epoxy resins that are hydrogen atoms, are available as commercially available products. In the epoxy resin represented by the following general formula (XI), ESN-175 (trade name, Nissian iron-gold chemical Co., Ltd.) in which i is 0, j is 0, and k is 0, and the like are commercially available.

[ solution 18]

In the formulae (X) and (XI), R³⁸The monovalent organic groups may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. R³⁷、R³⁹～R⁴¹The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i is an integer of 0 to 3, and j is an integer of 0 to 3And each k is an integer of 0 to 2, each k is independently an integer of 0 to 4, and each 1 is independently an integer of 0 to 6. n is an average value and is a number of 0 to 10 independently.

With respect to R in the general formulae (II) to (XI)⁸～R²¹And R³⁷～R⁴¹By "may be respectively the same or different" is meant for example 8 to 88R's in formula (II)⁸May be the same or different. With respect to the other R⁹～R²¹And R³⁷～R⁴¹It means that the numbers of the compounds contained in the formulae may be the same or different. In addition, R⁸～R²¹And R³⁷～R⁴¹May be the same or different. For example, R⁹And R¹⁰May be the same or different.

The organic group having 1 to 18 carbon atoms in the general formulae (III) to (XI) is preferably an alkyl group or an aryl group.

N in the general formulae (II) to (XI) is an average value, and preferably ranges from 0 to 10 independently. When n is 10 or less, the melt viscosity of the resin component is not excessively high, the viscosity of the curable resin composition is reduced during melt molding, and the occurrence of filling failure, deformation of bonding wires (metal wires connecting the element and the lead), and the like tends to be suppressed. More preferably, n is set in the range of 0 to 4.

The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is preferably 100 to 1000g/eq, more preferably 150 to 500g/eq, from the viewpoint of a balance among various properties such as moldability, reflow resistance, and electrical reliability.

The softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably from 40 ℃ to 180 ℃, and from the viewpoint of workability in the production of the curable resin composition, it is more preferably from 50 ℃ to 130 ℃.

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

(hardening agents other than the phenol novolak resin)

The type of the curing agent other than the specific phenol novolac resin contained in the curable resin composition is not particularly limited, and may be selected according to the type of the epoxy resin used in combination, the desired characteristics of the curable resin composition, and the like. Examples of the curing agent used in combination with the epoxy resin include: phenolic hardeners, amine hardeners, anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, and the like. From the viewpoint of both curability and pot life, at least one selected from the group consisting of a phenol curing agent, an amine curing agent, and an acid anhydride curing agent is preferable, and from the viewpoint of electrical reliability, a phenol curing agent is more preferable.

Examples of the phenol curing agent include a phenol resin and a polyphenol compound having two or more phenolic hydroxyl groups in 1 molecule. Specifically, there may be mentioned: polyhydric phenol compounds such as resorcinol, catechol, bisphenol a, bisphenol F, and substituted or unsubstituted biphenol; a novolak-type phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α -naphthol, β -naphthol, and dihydroxynaphthalene, with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, under an acidic catalyst; aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from the above phenolic compounds and dimethoxyp-xylene, bis (methoxymethyl) biphenyl and the like; p-xylene and/or m-xylene modified phenol resins; a melamine-modified phenol resin; terpene-modified phenol resin; dicyclopentadiene type phenol resins and dicyclopentadiene type naphthol resins synthesized by copolymerization of the phenolic compounds with dicyclopentadiene; a cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resins; a biphenyl type phenol resin; a triphenylmethane type phenol resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these. These phenol hardeners may be used alone or in combination of two or more.

Among the phenol hardeners, from the viewpoint of reflow resistance, at least one selected from the group consisting of an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, a copolymerized type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a novolak type phenol resin is preferable (these are referred to as "specific phenol hardeners"). The specific phenol curing agent may be used alone or in combination of two or more.

In the case where the curing agent contains the specific phenol curing agent, the content of the specific phenol curing agent is preferably 30% by mass or more, more preferably 50% by mass or more of the entire curing agent, from the viewpoint of sufficiently exhibiting the performance thereof

Examples of the aralkyl type phenol resin include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound and dimethoxyp-xylene, bis (methoxymethyl) biphenyl, and the like. The aralkyl type phenol resin may be further copolymerized with other phenol resins. As the copolymerized aralkyl type phenol resin, there can be exemplified: a phenol resin obtained by copolymerizing a benzaldehyde phenol resin and an aralkyl phenol resin, a phenol resin obtained by copolymerizing a salicylaldehyde phenol resin and an aralkyl phenol resin, a phenol resin obtained by copolymerizing a novolak phenol resin and an aralkyl phenol resin, and the like.

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

[ solution 19]

In the formulae (XII) to (XIV), R²³Represents a hydrogen atom or a carbon number of 1 to 18The monovalent organic groups may be the same or different. R²²、R²⁴、R²⁵And R²⁸The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. R²⁶And R²⁷The monovalent organic groups may be the same or different and each represents a hydroxyl group or a C1-18 monovalent organic group. i is independently an integer of 0 to 3, j is independently an integer of 0 to 2, k is independently an integer of 0 to 4, and p is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10 independently.

In the phenol resin represented by the general formula (XII), i is 0 and R²³MEH-7851 (trade name, Ming and Kangsha Co., Ltd.) and the like, which are hydrogen atoms, are available as commercially available products.

Of the phenol resins represented by the general formula (XIII), XL-225, XLC (trade name, manufactured by Mitsui chemical Co., Ltd.), MEH-7800 (trade name, manufactured by Ming and Kai chemical Co., Ltd.), and the like, which are i is 0 and k is 0, are commercially available.

In the phenol resin represented by the general formula (XIV), SN-170 (trade name, Nissin Corp. Chemicals Co., Ltd.) in which j is 0, k is 0, and p is 0, j is 0, k is 1, and R²⁷SN-395 (trade name, Nissin iron goddess chemical Co., Ltd.) or the like, which is a hydroxyl group and p is 0, is available as a commercially available product.

The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (product name) wherein i is 0, and the like are available as commercially available products.

[ solution 20]

In the formula (XV), R²⁹The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i independently represent an integer of 0 to 3. n is an average value, and represents 0 to10, in the drawing.

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 preferable.

Of the phenol resins represented by the following general formula (XVI), MEH-7500 (product name, Ming and Ka Co., Ltd.) in which i is 0 and k is 0, and the like are available as commercially available products.

[ solution 21]

In the formula (XVI), R³⁰And R³¹The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i is an integer of 0 to 3, and k is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

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

Of the phenol resins represented by the following general formula (XVII), HE-510 (trade name, Air Water chemistry, Inc.) in which i is 0, k is 0, and q is 0, and the like are available as commercially available products.

[ solution 22]

In the formula (XVII), R³²～R³⁴The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i is independently an integer of 0 to 3, k is independently an integer of 0 to 4, and q is independently an integer of 0 to 5. 1 and m are each an average value and are each independently a number of 0 to 11. Wherein the sum of 1 and m is a number of 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 an aldehyde compound with at least one phenolic compound selected from the group consisting of a phenol compound and a naphthol compound under an acidic catalyst. For example, a phenol resin represented by the following general formula (XVIII) is preferable.

In the phenol resin represented by the following general formula (XVIII), i is 0 and R³⁵Termamol (Tamanol)758, 759 (trade name, available from Desmodium chemical industries, Ltd.), HP-850N (trade name, available from Hitachi chemical industries, Ltd.), and the like, which are hydrogen atoms, are available as commercially available products.

[ solution 23]

In the formula (XVIII), R³⁵The monovalent organic groups may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. R³⁶The monovalent organic groups have 1 to 18 carbon atoms and may be the same or different. i independently represent an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

R in the general formula (XII) to (XVIII)²²～R³⁶The "may be the same or different" as defined in (A) means, for example, i R's in the formula (XII)²²May be the same or different from each other. With respect to the other R²³～R³⁶It means that the numbers of the compounds contained in the formulae may be the same or different from each other. In addition, R²²～R³⁶Each may be the same or different. For example, R²²And R²³Either the same or different, R³⁰And R³¹May be the same or different.

N in the general formulae (XII) to (XVIII) is preferably in the range of 0 to 10. If the viscosity is 10 or less, the melt viscosity of the resin component is not too high, the viscosity of the curable resin composition during melt molding is also low, and a filling failure does not occur or deformation of a bonding wire (a metal wire connecting a device and a lead) is less likely to occur. The average n in 1 molecule is preferably set to 0 to 4.

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

The softening point or melting point of the hardener is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably from 40 ℃ to 180 ℃, and from the viewpoint of workability in the production of the curable resin composition, it is more preferably from 50 ℃ to 130 ℃.

The equivalent ratio of the epoxy resin to 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 (the number of functional groups in the hardener/the number of functional groups in the epoxy resin) is not particularly limited. The amount of the unreacted components is preferably in the range of 0.5 to 2.0, more preferably 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferably set to a range of 0.8 to 1.2.

(hardening accelerator)

The curable resin composition may also contain a curing accelerator. The type of the curing accelerator is not particularly limited, and may be selected according to the type of the curable resin, the 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: tertiary phosphines such as triphenylphosphine, diphenyl (p-toluene) phosphine, tri (alkylphenyl) phosphine, tri (alkoxyphenyl) phosphine, tri (alkyl-alkoxyphenyl) phosphine, tri (dialkylphenyl) phosphine, tri (trialkylphenyl) phosphine, tri (tetraalkylphenyl) phosphine, tri (dialkoxyphenyl) phosphine, tri (trialkoxyphenyl) phosphine, tri (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine; a compound having intramolecular polarization formed by addition of a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, phenyl-1, 4-benzoquinone, or a compound having a pi bond such as diazophenylmethane; reacting the tertiary phosphine or the phosphine compound with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, a compound having intramolecular polarization obtained by reacting a halogenated phenol compound such as 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2, 6-dimethylphenol, 4-bromo-3, 5-dimethylphenol, 4-bromo-2, 6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4' -hydroxybiphenyl, and then dehydrohalogenating the resultant; tetra-substituted phosphonium such as tetraphenylphosphonium and tetra-substituted borate in which a phenyl group bonded to a boron atom is not present such as tetra-p-tolylborate; salts of a tetra-substituted phosphonium and an anion obtained by removing a proton from a phenol compound, salts of a tetra-substituted phosphonium and an anion obtained by removing a proton from a carboxylic acid compound, and the like.

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

[ solution 24]

In the formula (I-1), R¹～R³Each independently a C1-18 hydrocarbon group, R¹～R³Two or more of which may be bonded to each other to form a cyclic structure, R⁴～R⁷Each independently represents a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, R⁴～R⁷Two or more of them may be bonded to each other to form a ring structure.

R as formula (I-1)¹～R³The "hydrocarbon group having 1 to 18 carbon atoms" described herein includes aliphatic hydrocarbon groups having 1 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms.

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

The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or 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 preferable.

Specific examples of the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl and dodecyl, allyl, vinyl, and the like. The linear or branched aliphatic hydrocarbon group may or may not have a substituent. As the substituent, there may be mentioned: alkoxy groups such as methoxy, ethoxy, butoxy and tert-butoxy, aryl groups such as phenyl and naphthyl, 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 preferable, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable, and n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, and n-octyl group are further preferable.

Specific examples of the alicyclic hydrocarbon 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 have a substituent or may have no substituent. As the substituent, there may be mentioned: alkyl groups such as methyl, ethyl, butyl and tert-butyl, alkoxy groups such as methoxy, ethoxy, butoxy and tert-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, halogen atoms and the like. The alicyclic hydrocarbon group may have two or more substituents, and the substituents may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3 to 18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of hardening properties, an unsubstituted cycloalkyl group is preferable, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group, a cyclopentyl group, and a cycloheptyl group are further preferable.

The C6-18 aromatic hydrocarbon group is preferably C6-14, more preferably C6-10. The aromatic hydrocarbon group may have a substituent or may have no substituent. As the substituent, there may be mentioned: alkyl groups such as methyl, ethyl, butyl and tert-butyl, alkoxy groups such as methoxy, ethoxy, butoxy and tert-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, halogen atoms and the like. The aromatic hydrocarbon group may have two or more substituents, and the substituents may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6 to 18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

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

R as formula (I-1)¹～R³The term "R" as used herein¹～R³Two or more of which may be bonded to each other to form a cyclic structure "means that R¹～R³In which 2 or 3 bonds are present, and the entirety is a divalent or trivalent hydrocarbon group. As R at this time¹～R³Examples thereof include an alkylene group such as an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group, an alkenylene group such as an ethynylene group, a propynyl group, or a butynyl group, an aralkylene group such as a methylenephenylene group, an arylene group such as a phenylene group, a naphthylene group, or an anthracenylene group, and a substituent group capable of forming a cyclic structure by bonding to a phosphorus atom. These substitutionsThe group may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

As R in the general formula (I-1)⁴～R⁷The "organic group having 1 to 18 carbon atoms" described herein includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbyloxy group, an aromatic hydrocarbyloxy group, an acyl group, a hydrocarbyloxycarbonyl group, and an acyloxy group, each of which has 1 to 18 carbon atoms and may be substituted or unsubstituted.

Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group include R¹～R³Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group are described above.

Examples of the aliphatic hydrocarbon oxy group include: an oxy group having a structure in which an oxygen atom is bonded to the aliphatic hydrocarbon group, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a 2-butoxy group, a tert-butoxy group, a cyclopropoxy group, a cyclohexyloxy group, a cyclopentyloxy group, an allyloxy group, or a vinyloxy group; these aliphatic hydrocarbon oxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

As the aromatic alkoxy group, there may be mentioned: an oxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group, such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, or a phenoxyphenoxy group; these aromatic hydrocarbyloxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

Examples of the acyl group include: an aliphatic hydrocarbon carbonyl group such as a formyl group, an acetyl group, an ethylcarbonyl group, a butyryl group, a cyclohexylcarbonyl group, and an allylcarbonyl group, and an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group and a methylphenylcarbonyl group; these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

Examples of the hydrocarbyloxycarbonyl group include: aliphatic hydrocarbyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, allyloxycarbonyl and cyclohexyloxycarbonyl, aromatic hydrocarbyloxycarbonyl groups such as phenoxycarbonyl and methylphenoxycarbonyl, and groups in which these aliphatic hydrocarbylcarbonyloxy groups or aromatic hydrocarbylcarbonyloxy groups are further substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom or the like.

Examples of the acyloxy group include: aliphatic hydrocarbon carbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy and cyclohexylcarbonyloxy, aromatic hydrocarbon carbonyloxy such as phenylcarbonyloxy and methylphenylcarbonyloxy, and those substituted with alkyl, alkoxy, aryl, aryloxy, amino or halogen atom.

R as said general formula (I-1)⁴～R⁷The term "two or more R" as used herein⁴～R⁷Can be bonded to each other to form a cyclic structure "means 2 to 4R⁴～R⁷The bond, as a whole, may form a 2-4 valent organic group. As R at this time⁴～R⁷Examples thereof include an alkylene group such as an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group, an alkenylene group such as an ethynylene group, a propynyl group and a butynyl group, an aralkylene group such as a methylenephenylene group, an arylene group such as a phenylene group, a naphthylene group and an anthracenylene group, and a substituent which may form a cyclic structure, and an oxy group or a dioxy group thereof. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

R as said general formula (I-1)⁴～R⁷And is not particularly limited. For example, preferably independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. Among them, from the viewpoint of easiness of obtaining the raw material, a hydrogen atom, a hydroxyl group, an aryl group unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a linear or cyclic alkyl group is preferable. As the aryl group which is unsubstituted or substituted with at least one member selected from the group consisting of alkyl groups and alkoxy groups, phenyl group, p-tolyl group and m-toluene are mentionedAnd o-tolyl, p-methoxyphenyl, and the like. Examples of the linear or cyclic alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, an octyl group, and a cyclohexyl group. From the viewpoint of curability, R is preferable⁴～R⁷All being hydrogen atoms, or R⁴～R⁷At least one of them is a hydroxyl group, and the rest are all hydrogen atoms.

In the general formula (I-1), R is more preferably¹～R³Two or more of them are C1-18 alkyl or C3-18 cycloalkyl, R⁴～R⁷All are hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atoms. More preferably R¹～R³Wherein all of the groups are C1-18 alkyl or C3-18 cycloalkyl, R⁴～R⁷All are hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atoms.

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

[ solution 25]

In the formula (I-2), R¹～R³Each independently a C1-18 hydrocarbon group, R¹～R³Two or more of which may be bonded to each other to form a cyclic structure, R⁴～R⁶Each independently represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, R⁴～R⁶Two or more of them may be bonded to each other to form a ring structure.

R in the general formula (I-2)¹～R⁶Are respectively related to R in the general formula (I-1)¹～R⁶The specific examples of (A) are the same, and the preferable 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, an addition reaction product of tricyclohexylphosphine and 1, 4-benzoquinone, an addition reaction product of dicyclohexylphenylphosphine and 1, 4-benzoquinone, an addition reaction product of cyclohexyldiphenylphosphine and 1, 4-benzoquinone, an addition reaction product of triisobutylphosphine and 1, 4-benzoquinone, an addition reaction product of tricyclopentylphosphine and 1, 4-benzoquinone, and the like.

The specific hardening accelerator is obtained, for example, as an adduct of a third phosphine compound and a quinone compound.

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-trimethylphenyl) phosphine, tris (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

Specific examples of the quinone compound include: o-benzoquinone, p-benzoquinone, diphenoquinone, 1, 4-naphthoquinone, anthraquinone, and the like. P-benzoquinone is preferred from the viewpoint of moisture resistance and storage stability.

The curable resin composition may contain a curing accelerator other than the phosphonium compound.

Specific examples of the hardening accelerator other than the phosphonium compound include: diazabicycloalkenes such as 1, 5-Diazabicyclo [4.3.0] nonene-5 (1, 5-Diazabicyclo [4.3.0] nonene-5, DBN), 1, 8-Diazabicyclo [5.4.0] undecene-7 (1, 8-Diazabicyclo [5.4.0] undecene-7, DBU), and cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; a phenol novolac salt of the cyclic amidine compound or a derivative thereof; compounds having intramolecular polarization formed by adding a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, phenyl-1, 4-benzoquinone, or a compound having a pi bond such as diazophenylmethane to these compounds; cyclic amidinium compounds such as tetraphenylboron salt of DBU, tetraphenylboron salt of DBN, tetraphenylboron salt of 2-ethyl-4-methylimidazole and tetraphenylboron salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like; derivatives of the tertiary amine compounds; and ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide.

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

When the curable resin composition contains a curing accelerator, the amount of the curing accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component. When the amount of the curing accelerator is 0.1 part by mass or more per 100 parts by mass of the resin component, the curing accelerator tends to be cured well in a short time. If the amount of the curing accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, a good molded article having a curing rate not too high tends to be obtained.

(inorganic Filler)

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

The kind of the inorganic filler is not particularly limited. Specifically, there may be mentioned: inorganic materials such as fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica, and the like. Inorganic fillers having a flame retardant effect may also be used. Examples of the inorganic filler having a flame retardant effect include: and a composite metal hydroxide such as aluminum hydroxide, magnesium hydroxide, or a composite hydroxide of magnesium and zinc, zinc borate, and the like. Among them, fused silica is preferable from the viewpoint of a reduction in the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic filler may be used alone or in combination of two or more. 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, the content thereof is not particularly limited. From the viewpoint of fluidity and strength, the curable resin composition preferably has a volume of 30 to 90%, more preferably 35 to 80%, and still more preferably 40 to 70% of the entire curable resin composition. When the content of the inorganic filler is 30 vol% or more of the entire curable resin composition, the properties of the cured product, such as the thermal expansion coefficient, the thermal conductivity, and the elastic coefficient, tend to be further improved. When the content of the inorganic filler is 90 vol% or less of the entire curable resin composition, an increase in viscosity of the curable resin composition is suppressed, the flowability is further improved, and the moldability tends to be further improved.

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

The volume average particle diameter of the inorganic filler in the curable resin composition or the cured product thereof can be measured by a known method. For example, an inorganic filler is extracted from a self-curable resin composition or a cured product using an organic solvent, nitric acid, aqua regia, or the like, and sufficiently dispersed by an ultrasonic disperser or the like to prepare a dispersion. The volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured by a laser diffraction scattering particle size distribution measuring apparatus using the dispersion. Alternatively, the volume average particle diameter of the inorganic filler may be measured from a volume-based particle size distribution obtained by embedding a cured product in a transparent epoxy resin or the like, polishing the cured product to obtain a cross section, and observing the obtained cross section with a scanning electron microscope. Further, the measurement can be performed as follows: two-dimensional cross-sectional observation of the hardened material was continuously performed using a Focused Ion Beam (FIB) apparatus (Focused Electron Microscope (SEM)) or the like, and three-dimensional structural analysis was performed.

From the viewpoint of fluidity of the curable resin composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably distributed in a wide range.

[ various additives ]

The curable resin composition may contain, in addition to the above components, various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent, which are exemplified below. The curable resin composition may contain, in addition to the additives exemplified below, various additives known in the art as needed.

(coupling agent)

When the curable resin composition contains an inorganic filler, a coupling agent may be contained to improve the adhesion between the resin component and the inorganic filler. Examples of coupling agents include: known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureasilane and vinylsilane, titanium-based compounds, aluminum chelate compounds and aluminum/zirconium-based compounds.

When the curable resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass, per 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, the adhesion to the frame (frame) tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(ion exchanger)

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

Mg_(1-x)Al_X(OH)₂(CO₃)_X/2·mH₂O……(A)

(X is more than 0 and less than or equal to 0.5, and m is a positive number)

When the curable resin composition contains an ion exchanger, the content of the ion exchanger is not particularly limited as long as it is a sufficient amount for capturing halogen ions or the like. For example, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component.

(mold releasing agent)

The curable resin composition may contain a release agent from the viewpoint of obtaining good releasability from a mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include: and higher fatty acids such as carnauba wax (carnauba wax), octacosanoic acid, stearic acid, metal salts of higher fatty acids, ester waxes such as octacosanoic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.

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, per 100 parts by mass of the resin component. When the amount of the release agent is 0.01 parts by mass or more per 100 parts by mass of the resin component, sufficient releasability tends to be obtained. When the amount is 15 parts by mass or less, more favorable adhesion 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 flame retardants can be used. Specifically, examples thereof include organic or inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, and metal hydroxides. One kind of the flame retardant may be used alone, or two or more kinds may be used in combination.

In the case where the curable resin composition contains a flame retardant, the amount of the flame retardant is not particularly limited as long as the amount is sufficient for obtaining a desired flame retardant effect. For example, the amount is preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass, per 100 parts by mass of the resin component.

(coloring agent)

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, red lead, and iron oxide. The content of the colorant can be appropriately selected depending on the purpose and the like. The colorant may be used alone or in combination of two or more.

(stress relaxation Agents)

The curable resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By including a stress relaxation agent, the occurrence of warpage of the package and package cracks can be further reduced. As the stress relaxation agent, a commonly used known stress relaxation agent (flexibility agent) can be mentioned. Specifically, there may be mentioned thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers, rubber particles such as Natural Rubber (NR), acrylonitrile-butadiene rubber (NBR), acrylic rubber, urethane rubber, and silicone powder, and rubber particles having a core-shell structure such as methyl Methacrylate-styrene-butadiene copolymer (MBS), methyl Methacrylate-silicone copolymer, and methyl Methacrylate-butyl acrylate copolymer. The stress relaxation agent may be used alone or in combination of two or more. Among them, silicone-based stress relaxers are preferable. Examples of the silicone-based stress relaxation agent include silicone-based stress relaxation agents having epoxy groups, silicone-based stress relaxation agents having amino groups, and silicone-based stress relaxation agents obtained by polyether-modifying these agents.

(method for producing curable resin composition)

The method for preparing the curable resin composition is not particularly limited. The following methods can be mentioned as a general method: after the components are sufficiently mixed in a predetermined blending amount by a mixer or the like, the mixture is melt-kneaded by a grinding roll, an extruder or the like, cooled, and pulverized. More specifically, for example, the following methods can be mentioned: the prescribed amounts of the above components are uniformly stirred and mixed, kneaded and cooled by a kneader, roll, extruder or the like heated in advance to 70 to 140 ℃, and pulverized.

The curable resin composition is preferably a solid at normal temperature and normal pressure (e.g., 25 ℃ C., atmospheric pressure). The shape of the curable resin composition in the case of a solid is not particularly limited, and examples thereof include powder, granule, and tablet. From the viewpoint of workability, the size and mass of the curable resin composition in the form of a sheet are preferably those according to the molding conditions of the package.

< electronic component device >

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

As an electronic component device, there is exemplified an electronic component device in which an element section obtained by mounting an element (an active element such as a semiconductor chip, a transistor, a diode, or a thyristor, a passive element such as a capacitor, a resistor, or a coil, or the like) on a support member such as a lead frame, a wired carrier tape, a wiring board, glass, a silicon wafer, or an organic substrate is sealed with a curable resin composition.

More specifically, there may be mentioned: a general resin-sealed IC such as a Dual Inline Package (DIP), a Plastic Leaded Chip Carrier (PLCC), a Quad Flat Package (QFP), a Small Outline Package (SOP), a Small Outline J-lead Package (SOJ), a Thin Outline Package (TSOP), a Thin Quad Flat Package (TQFP), or the like, which has a structure in which after an element is fixed on a lead frame and a terminal portion and a lead portion of the element such as a bonding pad and the like are connected by wire bonding, a bump and the like, the terminal portion and the lead portion of the element are sealed by transfer molding or the like using a curable resin composition; a Tape Carrier Package (TCP) having a structure in which a component connected to a Carrier Tape by bumps is sealed with a curable resin composition; chip On Board (COB) modules, hybrid ICs, multi-Chip modules, and the like, which have a structure in which elements connected to wires formed On a support member by wire bonding, flip Chip bonding, solder, or the like are sealed with a curable resin composition; a Ball Grid Array (BGA), a Chip Size Package (CSP), a Multi-Chip Package (MCP), or the like, has a structure in which an element is mounted on a surface of a support member having terminals for wiring board connection formed on a back surface thereof, the element is connected to a wiring formed on the support member by bump or wire bonding, and then the element is sealed with a curable resin composition. In addition, a curable resin composition can also be preferably used for the printed wiring board.

Examples of the method for sealing the electronic component device with the curable resin composition include low-pressure transfer molding, injection molding, and compression molding. Of these, a low-pressure transfer molding method is generally used.

[ examples ]

The embodiments are described below in detail by way of examples, but the scope of the embodiments is not limited to these examples.

[ preparation of a curable resin composition ]

Curable resin compositions of examples 1 to 15 and comparative examples 1 to 8 were prepared by mixing the following materials in the compositions (parts by mass) shown in tables 1 and 2, and roll-kneading the mixture at a kneading temperature of 80 ℃ for 15 minutes.

(epoxy resin)

Epoxy resin 1: biphenyl type epoxy resin having an epoxy equivalent of 196g/eq and a melting point of 106 ℃ (trade name "YX-4000H" manufactured by Mitsubishi chemical corporation)

Epoxy resin 2: styrene-modified phenol novolak type epoxy resin having an epoxy equivalent of 282g/eq and a softening point of 59 ℃ (trade name "YDAN-1000-10C", available from Xinri Tokyo chemical Co., Ltd.)

Epoxy resin 3: methoxynaphthalene-cresol formaldehyde co-condensed type epoxy resin having an epoxy equivalent of 250g/eq and a softening point of 58 ℃ (trade name "HP-5000" from Diegon (DIC) Co., Ltd.)

Epoxy resin 4: aralkyl type epoxy resin having an epoxy equivalent of 282g/eq and a softening point of 56 ℃ and containing a biphenylene skeleton (trade name "NC-3000" from Nippon chemical Co., Ltd.)

(hardener in comparative example)

Hardening agent A: phenol aralkyl resin having a hydroxyl equivalent of 176g/eq and a softening point of 70 ℃ (product name "MEH-7800" from Ming and Heisha GmbH)

And (3) hardening agent B: phenol aralkyl resin having a biphenyl skeleton type with a hydroxyl equivalent of 199g/eq and a softening point of 89 ℃ (MEH-7851, product name of Ming and Hei Kagaku Co., Ltd.)

(hardening agent of example)

Specific phenol novolac resin 1: by using formaldehyde to R²A mixture of the aliphatic hydrocarbon groups represented by the group (A) and represented by the general formulae (1-1) to (1-3), i.e., cashew nut shell liquid (Cashew n)ut shell liquid) and phenol and a novolak resin having a hydroxyl equivalent of 223g/eq and a viscosity of 19.3 pas at 25 ℃ (trade name "ELP 83H" from Dogrong chemical industries, Ltd.)

Specific phenol novolac resin 2: by using formaldehyde to R²A novolak resin having a hydroxyl equivalent of 209g/eq obtained by polycondensation of an industrial cashew nut shell liquid, cresol and phenol, which is a mixture of the aliphatic hydrocarbon groups represented by the group (A) and represented by the general formulae (1-1) to (1-3), and having a viscosity of 14.0 pas at 25 ℃ (trade name "ELPC 80", manufactured by Jurison chemical industries, Ltd.)

Specific phenol novolac resin 3: by using formaldehyde to R²A novolak resin having a hydroxyl equivalent of 204g/eq obtained by polycondensation of an industrial cashew shell liquid, cresol and phenol, which is a mixture of the aliphatic hydrocarbon groups represented by the group (A) and represented by the general formulae (1-1) to (1-3), and having a viscosity of 23.6 pas at 25 ℃ (trade name "ELPC 75", manufactured by Jurison chemical industries, Ltd.)

Specific phenol novolac resin 4: by using formaldehyde to R²A novolak resin having a hydroxyl equivalent of 204g/eq obtained by polycondensation of an industrial cashew shell liquid and cresol, which is a mixture of the aliphatic hydrocarbon groups represented by the group (A) and represented by the general formulae (1-1) to (1-3) (trade name "ELC 75" available from Jur chemical industries, Ltd.) and having a viscosity of 20.2 pas at 25 ℃)

(hardening 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)

Epoxy silane (gamma-glycidoxypropyltrimethoxysilane)

(coloring agent)

Carbon Black (Mitsubishi chemical corporation, trade name "MA-100")

(mold releasing agent)

Carnauba wax (Cerarica NODA, Inc.)

[ Table 1]

[ Table 2]

[ evaluation of curable resin composition ]

The properties of the curable resin compositions prepared in examples 1 to 15 and comparative examples 1 to 8 were evaluated by the following property tests. The evaluation results are shown in tables 3 and 4. Unless otherwise indicated, the curable resin composition was molded by a transfer molding machine at a mold temperature of 175 ℃, a molding pressure of 6.9MPa, and a curing time of 90 seconds. Further, post-curing was carried out at 175 ℃ for 5 hours, if necessary.

(1) Rotational flow

The curable resin composition was molded under the above conditions using a mold for measuring rotational flow according to EMMI-1-66 to determine the flow distance (cm).

(2) Hot hardness

The curable resin composition was molded under the above conditions into a disk having a diameter of 50mm × a thickness of 3mm, and immediately after molding, the disk was measured using a Shore D durometer (HD-1120 (D type, manufactured by Shanghai Co., Ltd.).

(3)260 ℃ shear adhesion

A curable resin composition was molded on a copper alloy plate (Pd-PPF) under the above conditions in such a size that the bottom surface had a diameter of 4mm, the top surface had a diameter of 3mm, and the height was 4mm, and post-curing was performed under the above conditions. Thereafter, the shear adhesion (MPa) was determined at a shear rate of 50 μm/s while maintaining the temperature of the copper plate at 260 ℃ using a bonding tester (Bondtester) (Japan Dage Japan Ltd., Series (Series) 4000).

(4) Water absorption rate

Post-hardening the circular plate formed in (2) under the conditions. Thereafter, the obtained disk was left to stand at 85 ℃ and 60% RH for 168 hours, and the change in mass before and after the standing was measured. The water absorption was calculated from the measurement results by the following formula.

Water absorption (% by mass) is (mass of disk after leaving-mass of disk before leaving)/mass of disk before leaving × 100

(5) Reflow resistance

An 80-pin flat package (QFP) (lead frame material: copper alloy (Pd-PPF)) having an external dimension of 20mm × 14mm × 2mm and loaded with a silicon chip of 8mm × 10mm × 0.4mm was molded using a curable resin composition under the above conditions, and post-cured under the above conditions. The obtained capsules were humidified at 85 ℃ and 60% RH for 168 hours. Thereafter, reflow treatment was performed at a predetermined temperature (250 ℃, 260 ℃, 270 ℃) for 10 seconds to visually observe the presence or absence of cracks outside the package, and the presence or absence of peeling inside the package was observed with an ultrasonic flaw detector (HYE-FOCUS, manufactured by hitachi corporation). Reflow resistance was evaluated as the sum of the number of packages that had cracked or peeled off relative to the number of packages tested (10).

[ Table 3]

[ Table 4]

As shown in tables 3 and 4, examples 1 to 15 containing the specific phenol novolac resin 1 to 4 have improved adhesion to metal (Pd-PPF) and improved reflow resistance, as compared to comparative examples 1 to 8 containing no specific phenol novolac resin.

Claims

1. A curable resin composition comprising an epoxy resin and a curing agent, wherein the curing agent comprises a phenol novolac resin containing a structural unit derived from a phenol compound represented by the following general formula (1);

[ solution 1]

(in the general formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2).

2. The curable resin composition according to claim 1, wherein the phenol novolac resin contains at least one of structural units derived from phenol compounds represented by the following general formulae (1-1) to (1-3) as a structural unit derived from a phenol compound represented by the general formula (1);

[ solution 2]

In (general formula (1-1) to (1-3), R²And R in the general formula (1)²Are the same meaning).

3. The curable resin composition according to claim 1 or 2, wherein the phenol novolac resin further comprises a structural unit derived from a phenol compound other than the phenol compound represented by the general formula (1).

4. The curable resin composition according to any one of claims 1 to 3, wherein the curing agent further comprises a curing agent other than a phenol novolac resin containing a structural unit derived from the phenol compound represented by the general formula (1).

5. The curable resin composition according to any one of claims 1 to 4, which is used as a sealing material for electronic component devices.

6. An electronic part device comprising: an element; and a cured product of the curable resin composition according to any one of claims 1 to 5 sealing the element.