Curable resin composition and electronic component device

Abstract

To provide a curable resin composition capable of obtaining a sealing structure excellent in adhesiveness to a metal and reflow resistance, and an electronic component device obtained by using the same.SOLUTION: A curable resin composition comprising an epoxy resin and a curing agent, wherein the curing agent comprises a phenol novolac resin comprising a structural unit derived from a phenol compound represented by the following general formula (1): In General Formula (1), R1 represents hydrogen or methyl, R2 represents an aliphatic hydrocarbyl group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, as electronic devices have become smaller, lighter, and more powerful, the density of packaging has increased. As a result, the mainstream of electronic component devices is shifting from conventional pin insertion type packages to surface mount type packages for ICs (Integrated Circuits), LSIs (Large Scale Integration), etc.

[0003] Surface-mount packages differ from conventional pin-insertion packages in their mounting method. Specifically, when attaching pins to a wiring board, conventional pin-insertion packages require soldering from the backside of the board after the pins are inserted into the board. This prevents the package from being directly exposed to high temperatures. However, with surface-mount packages, the entire electronic device is processed using a solder bath or reflow equipment, exposing the package directly to soldering (reflow) temperatures. As a result, if the package absorbs moisture, the moisture rapidly expands during soldering. The resulting vapor pressure acts as a peel stress, causing peeling between the insert (e.g., chip, lead frame) and the encapsulant, potentially resulting in package cracks and poor electrical characteristics. Therefore, there is a need for encapsulating materials that offer excellent adhesion to the insert and, ultimately, excellent solder heat resistance (reflow resistance).

[0004] To meet the above demands, for example, the use of silane coupling agents as modifiers for inorganic fillers contained in sealing materials has been investigated. Specifically, the use of epoxy group-containing silane coupling agents or amino group-containing silane coupling agents (see, for example, Patent Document 1), the use of sulfur atom-containing silane coupling agents (see, for example, Patent Document 2), etc. has been investigated. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-147939 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-103940 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the method using an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent may not be effective enough in improving adhesion to the metal on the surface of the lead frame, and the method using a sulfur atom-containing silane coupling agent has the problem of not being effective enough in improving adhesion to specific metals such as gold and silver.

[0007] 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 that has excellent adhesion to metals and reflow resistance, and an electronic component device that can be obtained using the same. [Means for solving the problem]

[0008] The means for solving the above 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):

[0009] [ka] (In general formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2. <2> The phenol novolak resin contains, as a structural unit derived from the phenol compound represented by the general formula (1), at least one structural unit derived from a phenol compound represented by the following general formulas (1-1) to (1-3): <1> The curable resin composition according to claim 1.

[0010] [ka] (In the general formulas (1-1) to (1-3), R 2 is R in general formula (1) 2 is equivalent to <3> the phenol novolak resin further contains a structural unit derived from a phenol compound other than the phenol compound represented by general formula (1); <1> or <2> The curable resin composition according to claim 1. <4> the curing agent further includes a curing agent other than a phenol novolac resin containing a structural unit derived from a phenol compound represented by the general formula (1); <1> ~ <3> The curable resin composition according to any one of the above. <5> For use as an encapsulant for electronic component devices, <1> ~ <4> The curable resin composition according to any one of the above. <6> an element and a device for sealing the element; <1> ~ <5> and an electronic component device comprising a cured product of the curable resin composition according to any one of claims 1 to 4. [Effects of the Invention]

[0011] According to the present invention, there are provided a curable resin composition that can provide a sealing structure that has excellent adhesion to metals and reflow resistance, and an electronic component device obtained using the same. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present invention.

[0013] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the present disclosure, in the numerical ranges described in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the described numerical ranges, the upper or lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, the content or amount of each component in a composition means, when multiple substances corresponding to each component are present in the composition, the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the particle size of each component in a composition means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified, when multiple types of particles corresponding to each component are present in the composition.

[0014] <Curable resin composition> The curable resin composition of the present disclosure includes an epoxy resin and a curing agent, and the curing agent includes a phenol novolac resin (hereinafter also referred to as a specific phenol novolac resin) containing a structural unit derived from a phenol compound represented by the following general formula (1):

[0015] [ka]

[0016] In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

[0017] Curable resin compositions containing specific phenol novolac resins have excellent adhesion to metals (especially gold) in a cured state. The reason for this is not entirely clear, but it is thought that, for example, the aliphatic hydrocarbon group having 10 to 18 carbon atoms contained in the structural unit derived from the phenol compound contained in the specific phenol novolac resin acts to improve adhesion to metals. Furthermore, it is thought that the aliphatic hydrocarbon group having 10 to 18 carbon atoms contained in the structural unit derived from the phenol compound contained in the specific phenol novolac resin acts to reduce the elastic modulus and water absorption rate near the interface between the metal surface and the cured product of the curable resin composition, thereby improving reflow resistance.

[0018] The curable resin composition containing the specific phenol novolac resin has excellent adhesion to metals in a cured state, and is therefore suitable as an encapsulant for a package including a lead frame whose surface is made of metal (particularly gold). An example of a lead frame whose surface is made of gold is a copper lead frame called PPF (Pre-Plating Lead Frame) that is plated with Ni-Pd-Au.

[0019] (Specific phenol novolac 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).

[0020] [ka]

[0021] In general formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 1 or 2.

[0022] The structural units derived from the phenol compound represented by general formula (1) contained in the specific phenol novolac resin may all have the same structure or may be different from one another. When the specific phenol novolac resin contains two or more types of structural units derived from the phenol compound represented by general formula (1), the arrangement of these units is not particularly limited and they may be arranged regularly or irregularly.

[0023] In one embodiment, the specific phenol novolak resin may contain at least a structural unit (monohydric phenol) where n is 1 and a structural unit (dihydric phenol) where n is 2 as structural units derived from a phenol compound represented by general formula (1), or may contain at least a structural unit (monohydric phenol) where n is 1 and a structural unit where n is 2 in which one hydroxyl group is in the meta position relative to the other hydroxyl group.

[0024] The specific phenol novolak resin may contain at least one of the structural units derived from the phenol compounds represented by the following general formulas (1-1) to (1-3) as the structural unit derived from the phenol compound represented by general formula (1), or may contain all of the structural units derived from the phenol compounds represented by general formulas (1-1) to (1-3).

[0025] [ka]

[0026] In the general formulas (1-1) to (1-3), R 2 is R in general formula (1) 2 is synonymous with.

[0027] In general formula (1), R 2The aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by the formula (I) may be an aliphatic hydrocarbon group having 13 to 16 carbon atoms, and may or may not have an unsaturated double bond. 2 When the aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by the formula (I) has an unsaturated double bond, the number of unsaturated double bonds is not particularly limited, and may be, for example, 1 to 5. 2 The aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by the formula (I) may be branched or unbranched, but is preferably unbranched. 2 Specific examples of the aliphatic hydrocarbon group having 10 to 18 carbon atoms represented by the formula (A) include the aliphatic hydrocarbon groups represented by the following group (A) (* indicates the bonding position to the aromatic ring). 2 The structures of the aliphatic hydrocarbon groups having 10 to 18 carbon atoms represented by the formula may be the same or different.

[0028] [ka]

[0029] The specific phenol novolak resin may further contain a structural unit derived from a phenol compound other than the phenol compound represented by general formula (1). Examples of the phenol compound other than the phenol compound represented by general formula (1) include phenol compounds represented by the following general formula (2).

[0030] [ka]

[0031] In general formula (2), R 1 represents a hydrogen atom or a methyl group, and n is an integer of 1 or 2. Examples of phenol compounds represented by general formula (2) include monohydric phenol compounds such as phenol and cresol, and dihydric phenol compounds such as resorcinol, catechol and hydroquinone.

[0032] In one embodiment, the specific phenol novolak resin may contain either or both of phenol and cresol as structural units derived from the phenol compound represented by general formula (2), or may contain either or both of phenol and orthocresol.

[0033] When the specific phenol novolac resin contains structural units derived from a phenol compound other than the phenol compound represented by general formula (1), the proportion of the structural units derived from the phenol compound represented by general formula (1) in the entire specific phenol novolac resin is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more.

[0034] The method for synthesizing the specific phenol novolac resin is not particularly limited. For example, the specific phenol novolac resin can be synthesized by reacting a phenol compound, which is a raw material for the specific phenol novolac resin, with an aldehyde such as formaldehyde in the presence of an acid catalyst.

[0035] The molecular weight of the specific phenol novolac resin is not particularly limited, and may have a weight average molecular weight in the range of 300 to 20,000 as measured by gel permeation chromatography, for example.

[0036] The viscosity of the specific phenol novolac resin is not particularly limited. For example, the viscosity at 25°C is preferably 50 Pa·s or less, and more preferably 30 Pa·s or less. The viscosity of the specific phenol novolac resin at 25°C is determined by multiplying the measured value (Pa·s) by a predetermined conversion factor (0.5) when rotating the resin at 10 rpm for 1 minute at 25°C using an EHD rotational viscometer equipped with a cone rotor having a cone angle of 3° and a cone radius of 14 mm.

[0037] The hydroxyl group equivalent of the specific phenol novolac resin is not particularly limited, but from the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0038] The specific phenol novolac resin is preferably used in combination with a curing agent other than the specific phenol novolac resin. That is, the curable resin composition preferably contains the specific phenol novolac resin as a curing agent and a curing agent other than the specific phenol novolac resin.

[0039] When the curable resin composition contains a specific phenol novolac resin as a curing agent and a curing agent other than the specific phenol novolac resin, from the viewpoint of curability, 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 improving adhesion to metal, the proportion of the specific phenol novolac resin in the entire curing agent is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more, on an equivalent basis.

[0040] The type of curing agent other than the specific phenol novolac resin is not particularly limited and can be selected depending on the desired properties of the curable resin composition, etc. Specific examples of the curing agent will be described later.

[0041] (epoxy resin) The type of epoxy resin contained in the curable resin composition is not particularly limited, and can be selected depending on the desired properties of the curable resin composition. Specific examples of epoxy resins include novolac epoxy resins (phenol novolac epoxy resins, orthocresol novolac epoxy resins, etc.) obtained by epoxidizing novolac resins obtained by condensing or co-condensing, under an acidic catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc.; triphenylmethane epoxy resins obtained by epoxidizing triphenylmethane phenolic resins obtained by condensing or co-condensing, under an acidic catalyst, the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc.; and novolac resins obtained by co-condensing, under an acidic catalyst, the above-mentioned phenolic compound and naphthol compound with an aldehyde compound. diphenylmethane-type epoxy resins, which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins, which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins, which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing epoxy resins, which are diglycidyl ethers of bisphenol S, etc.; epoxy resins, which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins, which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins, in which the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; and dicyclopentadiene-type epoxy resins, which are epoxidized co-condensation resins of dicyclopentadiene and phenolic compounds.Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are produced by epoxidizing the olefin bonds in the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include pentadiene-modified epoxy resins, cyclopentadiene-modified epoxy resins, which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Further examples of suitable epoxy resins include epoxidized silicone resins and epoxidized acrylic resins. These epoxy resins may be used alone or in combination of two or more.

[0042] Among the above epoxy resins, from the viewpoint of a balance between reflow resistance and fluidity, epoxy resins selected from the group consisting of biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur-atom-containing epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, copolymer-type epoxy resins, and aralkyl-type epoxy resins (these are referred to as "specific epoxy resins"). The specific epoxy resins may be used alone or in combination of two or more.

[0043] When the epoxy resin contains a specific epoxy resin, the content of the specific epoxy resin is preferably 30% by mass or more, and more preferably 50% by mass or more, of the total epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin.

[0044] Among the specific epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, and sulfur-atom-containing epoxy resins are more preferred from the viewpoint of fluidity, and dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, and aralkyl-type epoxy resins are preferred from the viewpoint of heat resistance. Specific examples of preferred epoxy resins are shown below.

[0045] 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. Among the epoxy resins represented by the following general formula (II), R 8 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 8 YX-4000H (Mitsubishi Chemical Corporation, product name) where R is a hydrogen atom, 8 4,4'-bis(2,3-epoxypropoxy)biphenyl, where R is a hydrogen atom, 8 When is a hydrogen atom and R 8 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 8 is a hydrogen atom, YL-6121H (trade name, Mitsubishi Chemical Corporation) and the like are commercially available.

[0046] [ka]

[0047] In formula (II), R 8represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, and may all be the same or different. n is an average value and represents a number of 0 to 10.

[0048] 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. Among the epoxy resins represented by the following general formula (III), R 9 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 9 is a hydrogen atom, and R 10 are all hydrogen atoms, and R 9 Three of the 3, 3', 5, and 5' positions are methyl groups, one is a t-butyl group, and the remaining R 9 is a hydrogen atom, and R 10 A mixture of 1 and 2 in which all of the above are hydrogen atoms is commercially available as ESLV-210 (product name, Sumitomo Chemical Co., Ltd.).

[0049] [ka]

[0050] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number of 0 to 10.

[0051] 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. Among the epoxy resins represented by the following general formula (IV), R 11 are all hydrogen atoms, and R 12 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 12YSLV-80XY (Nippon Steel Sumikin Chemical Co., Ltd., trade name) in which is a hydrogen atom is commercially available.

[0052] [ka]

[0053] In formula (IV), R 11 and R 12 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number of 0 to 10.

[0054] The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) can be mentioned. Among the epoxy resins represented by the following general formula (V), R 13 When the oxygen atom is substituted at the 4 and 4' positions, the 3 and 3' positions are t-butyl groups, and the 6 and 6' positions are methyl groups. 13 YSLV-120TE (Nippon Steel Sumikin Chemical Co., Ltd., trade name) in which ≡ is a hydrogen atom is commercially available.

[0055] [ka]

[0056] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number of 0 to 10.

[0057] The novolac epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac phenolic resin. For example, epoxy resins obtained by epoxidizing a novolac phenolic resin such as a phenol novolac resin, a cresol novolac resin, or a naphthol novolac resin using a method such as glycidyl etherification are preferred, and epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), R 14 are all hydrogen atoms, and R 15 is a methyl group, and i=1; ESCN-190, ESCN-195 (product names of Sumitomo Chemical Co., Ltd.); 14 are all hydrogen atoms and i=0, N-770 and N-775 (trade names, DIC Corporation), R 14 are all hydrogen atoms, and the part where i=0 and the part where i=1 are R 15 but- YDAN-1000-10C (Nippon Steel Sumikin Chemical Co., Ltd., product name), a styrene-modified phenolic novolac epoxy resin having a moiety of CH(CH3)-Ph, 14 are all hydrogen atoms, i=1, and R 15 is a methyl group and i=2, R 15 HP-5600 (trade name, DIC Corporation), which is a benzyl-modified cresol novolac epoxy resin having one methyl group and one benzyl group, is commercially available.

[0058] [ka]

[0059] In formula (VI), R 14 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 15 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0060] 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, DIC Corporation), in which i = 0, is commercially available.

[0061] [ka]

[0062] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0063] The triphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherifying a triphenylmethane phenolic resin, such as a novolac phenolic resin made from a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group, is preferred, and an epoxy resin represented by the following general formula (VIII) is more preferred. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and EPPN-502H (Nippon Kayaku Co., Ltd., trade name), in which i is 0 and k is 0, are commercially available.

[0064] [ka]

[0065] In formula (VIII), R 17 and R 18 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3, and each k independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10.

[0066] 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 made from a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, an epoxy resin obtained by glycidyl etherifying a novolac phenolic 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. Among the epoxy resins represented by the following general formula (IX), R 21 is a methyl group, i is 1, j is 0, and k is 0, and NC-7300 (trade name, Nippon Kayaku Co., Ltd.) is available as a commercially available product.

[0067] [ka]

[0068] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3, each j independently represents an integer of 0 to 2, and each k independently represents an integer of 0 to 4. Each l and m is an average value and a number of 0 to 10, and (l+m) represents a number of 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either formula (IX-1) or (IX-2) below. In formulas (IX-1) and (IX-2), R 19 ~R 21 The definitions of i, j and k are R in formula (IX). 19 ~R 21 has the same definition as i, j, and k. n is 1 (when bonding via a methylene group) or 0 (when bonding not via a methylene group).

[0069] [ka]

[0070] Examples of the epoxy resin represented by the general formula (IX) include random copolymers containing l structural units and m structural units randomly, alternating copolymers containing them alternately, copolymers containing them regularly, block copolymers containing them in block form, etc. Any of these may be used alone or in combination of two or more.

[0071] Another preferred copolymerized epoxy resin is Epiclon HP-5000 (trade name, DIC Corporation), a methoxynaphthalene-cresol-formaldehyde co-condensation epoxy resin containing the following two structural units in a random, alternating, or block order, and represented by the following general formula: In the following general formula, n and m each represent an average value and a number from 0 to 10, and (n+m) represents a number from 0 to 10, preferably n and m each represent an average value and a number from 1 to 9, and (n+m) represents a number from 2 to 10.

[0072] [ka]

[0073] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin made from a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, an epoxy resin obtained by glycidyl etherifying a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof is preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

[0074] Among the epoxy resins represented by the following general formula (X), those in which i is 0 and R 38is a hydrogen atom, i is 0, and R 38 is a hydrogen atom and all R 8 CER-3000 (trade name, Nippon Kayaku Co., Ltd.), which is a mixture of an epoxy resin in which i is a hydrogen atom and an epoxy resin in which k is a hydrogen atom at a mass ratio of 80:20, is commercially available. Furthermore, among the epoxy resins represented by the following general formula (XI), ESN-175 (trade name, Nippon Steel & Sumikin Chemical Co., Ltd.), in which i is 0, j is 0, and k is 0, is commercially available.

[0075] [ka]

[0076] In formulas (X) and (XI), R 38 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 37 , R 39 ~R 41 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each l is independently an integer of 0 to 6. Each n is an average value and is independently a number of 0 to 10.

[0077] R in the above general formulas (II) to (XI) 8 ~R 21 and R 37 ~R 41 In the formula (II), "all of them may be the same or different" means, for example, that 8 to 88 R 8 This means that all of the R may be the same or different. 9 ~R 21 and R 37 ~R 41 In addition, the numbers of R may all be the same or different. 8 ~R 21 and R 37~R 41 may be the same or different. For example, R 9 and R 10 may all be the same or different. In addition, 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.

[0078] In the general formulas (II) to (XI), n is an average value, and each independently is preferably in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the curable resin composition during melt molding tends to decrease, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting elements to leads), etc. is more preferably set in the range of 0 to 4.

[0079] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of a balance of various properties such as moldability, 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.

[0080] The softening point or melting point of the epoxy resin is not particularly limited, but is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of handleability during preparation of the curable resin composition.

[0081] The content of the epoxy resin in the curable resin composition is preferably 0.5 to 50 mass %, more preferably 2 to 30 mass %, from the viewpoints of strength, fluidity, heat resistance, moldability, etc.

[0082] (hardeners other than specific phenol novolac resins) The type of curing agent other than the specific phenol novolac resin contained in the curable resin composition is not particularly limited and can be selected depending on the type of epoxy resin used in combination, the desired properties of the curable resin composition, etc. Examples of curing agents used in combination with the epoxy resin include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. From the viewpoint of achieving both curability and pot life, at least one selected from the group consisting of phenol curing agents, amine curing agents, and acid anhydride curing agents is preferred, and from the viewpoint of electrical reliability, phenol curing agents are more preferred.

[0083] Examples of phenolic curing agents include phenolic resins and polyhydric phenolic compounds having two or more phenolic hydroxyl groups per molecule. Specific examples include polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic 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 an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; and copolymers of the above-mentioned phenolic compounds with dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. Examples of suitable phenolic curing agents include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from the above compounds; paraxylylene- and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used alone or in combination of two or more.

[0084] Among phenolic curing agents, from the viewpoint of reflow resistance, at least one selected from the group consisting of aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, triphenylmethane-type phenolic resins, copolymerized phenolic resins of benzaldehyde-type phenolic resins and aralkyl-type phenolic resins, and novolac-type phenolic resins (these are referred to as "specific phenolic curing agents"). The specific phenolic curing agents may be used alone or in combination of two or more.

[0085] When the curing agent contains a specific phenol curing agent, the content of the specific phenol curing agent is preferably 30% by mass or more, and more preferably 50% by mass or more, of the entire curing agent, from the viewpoint of fully exhibiting its performance.

[0086] Examples of aralkyl phenolic resins include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. The aralkyl phenolic resin may be further copolymerized with other phenolic resins. Examples of copolymerized aralkyl phenolic resins include copolymerized phenolic resins of benzaldehyde phenolic resins and aralkyl phenolic resins, copolymerized phenolic resins of salicylaldehyde phenolic resins and aralkyl phenolic resins, and copolymerized phenolic resins of novolac phenolic resins and aralkyl phenolic resins.

[0087] The aralkyl phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one compound selected from the group consisting of phenol compounds and naphthol compounds, and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, phenolic resins represented by the following general formulas (XII) to (XIV) are preferred.

[0088] [ka]

[0089] In formulas (XII) to (XIV), R 23 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 22 , R 24 , R 25 and R 28 R represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 26 and R 27 represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, and each j is Each k is independently an integer of 0 to 4, and each p is independently an integer of 0 to 4. n is an average value and is independently a number of 0 to 10.

[0090] Among the phenolic resins represented by the general formula (XII), i is 0 and R 23 MEH-7851 (product name, Meiwa Kasei Co., Ltd.), in which all are hydrogen atoms, is commercially available.

[0091] Among the phenolic resins represented by the general formula (XIII) above, XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Chemical Industry Co., Ltd., trade name), etc., in which i is 0 and k is 0, are commercially available.

[0092] Among the phenolic resins represented by the general formula (XIV), SN-170 (trade name, Nippon Steel & Sumikin Chemical Co., Ltd.) in which j is 0, k is 0, and p is 0, and R 27 is a hydroxyl group and p is 0, and SN-395 (trade name, Nippon Steel Sumikin Chemical Co., Ltd.) is available as a commercially available product.

[0093] The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XV) is preferred. Among the phenolic resins represented by the following general formula (XV), DPP (trade name, Nippon Petrochemical Co., Ltd.), in which i is 0, is commercially available.

[0094] [ka]

[0095] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0096] The triphenylmethane type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a triphenylmethane skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferred.

[0097] Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (trade name, Meiwa Kasei Co., Ltd.), in which i and k are 0, is commercially available.

[0098] [ka]

[0099] In formula (XVI), R 30 and R 31 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, and each k is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0100] The copolymerized phenolic resin of a benzaldehyde type phenolic resin and an aralkyl type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of a phenolic resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenolic resin. For example, a phenolic resin represented by the following general formula (XVII) is preferred.

[0101] Among the phenolic resins represented by the following general formula (XVII), HE-510 (trade name, Air Water Chemical Co., Ltd.), in which i is 0, k is 0, and q is 0, is commercially available.

[0102] [ka]

[0103] In formula (XVII), R 32 ~R 34 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, each k is independently an integer of 0 to 4, and each q is independently an integer of 0 to 5. Each l and m is an average value and independently a number of 0 to 11, provided that the sum of l and m is a number of 1 to 11.

[0104] The novolac phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds with an aldehyde compound in the presence of an acid catalyst. For example, a phenolic resin represented by the following general formula (XVIII) is preferred.

[0105] Among the phenolic resins represented by the following general formula (XVIII), those in which i is 0 and R 35 are all hydrogen atoms, such as Tamanol 758 and 759 (trade names, manufactured by Arakawa Chemical Industries, Ltd.) and HP-850N (trade name, manufactured by Hitachi Chemical Co., Ltd.).

[0106] [ka]

[0107] In formula (XVIII), R 35 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 36 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0108] R in the above general formulas (XII) to (XVIII) 22 ~R 36 The expression "may be the same or different" means, for example, that i R 22 This means that all of the R may be the same or different from each other. 23 ~R 36 In addition, the numbers of R may be the same or different from each other. 22 ~R 36 may be the same or different. For example, R 22 and R 23 may be the same or different, and R 30 and R 31 may all be the same or different.

[0109] In the general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the curable resin composition during melt molding will also be low, making it less likely that unfilled defects or deformation of bonding wires (gold wires connecting elements to leads) will occur. The average n in one molecule is preferably set in the range of 0 to 4.

[0110] The functional group equivalent of the curing agent (hydroxyl group equivalent in the case of a phenolic curing agent) is not particularly limited, but from the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0111] The softening point or melting point of the curing agent is not particularly limited, but is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of handleability during production of the curable resin composition.

[0112] The equivalent ratio of the epoxy resin to the curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent / number of functional groups in the epoxy resin), is not particularly limited. In order to minimize the amount of unreacted components, it is preferably set in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.3. From the viewpoints of moldability and reflow resistance, it is even more preferably set in the range of 0.8 to 1.2.

[0113] (curing accelerator) The curable resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited and can be selected depending on the type of curable resin, the desired properties of the curable resin composition, and the like.

[0114] From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound.Specific examples of phosphonium compounds include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkoxyphenyl compounds having intramolecular polarization obtained by adding a tertiary phosphine such as alkylarylphosphine, dialkylarylphosphine or alkyldiarylphosphine to a compound having a π bond 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 or phenyl-1,4-benzoquinone, or diazophenylmethane; The fin compounds 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-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 Examples of compounds include compounds having intramolecular polarization obtained by reacting a halogenated phenol compound such as 4-bromo-4'-hydroxybiphenyl with a halogenated phenol compound, followed by a dehydrohalogenation step; tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetra-substituted phosphonium compounds and tetra-substituted borates that do not have a phenyl group bonded to the boron atom, such as tetra-p-tolylborate; salts of tetra-substituted phosphonium compounds with anions obtained by removing a proton from a phenol compound, and salts of tetra-substituted phosphonium compounds with anions obtained by removing a proton from a carboxylic acid compound.

[0115] Among the above phosphonium compounds, the compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator) is preferred.

[0116] [ka]

[0117] In formula (I-1), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 Two or more of R may be bonded to each other to form a cyclic structure; 4 ~R 7 teeth , each independently represents a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms; R 4 ~R 7 Two or more of these may be bonded to each other to form a cyclic structure.

[0118] R in general formula (I-1) 1 ~R 3 The "hydrocarbon group having 1 to 18 carbon atoms" described above includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0119] From the viewpoint of flowability, the aliphatic hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.

[0120] The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.

[0121] Specific examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, as well as allyl and vinyl groups. The linear or branched aliphatic hydrocarbon groups may or may not have a substituent. Examples of the substituent include alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, and halogen atoms. The linear or branched aliphatic hydrocarbon groups may have two or more substituents, and in such cases, the substituents 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 curability, unsubstituted alkyl groups are preferred, unsubstituted alkyl groups having 1 to 8 carbon atoms are more preferred, and n-butyl, isobutyl, n-pentyl, n-hexyl and n-octyl groups are even more preferred.

[0122] Specific examples of alicyclic hydrocarbons having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl. The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, butyl, and tert-butyl; alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy; aryl groups such as phenyl and naphthyl; hydroxyl groups; amino groups; and halogen atoms. The alicyclic hydrocarbon group may have two or more substituents, and in such cases, 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 curability, unsubstituted cycloalkyl groups are preferred, unsubstituted cycloalkyl groups having 4 to 10 carbon atoms are more preferred, and cyclohexyl, cyclopentyl and cycloheptyl groups are even more preferred.

[0123] The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, butyl, and t-butyl; alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy; aryl groups such as phenyl and naphthyl; hydroxyl groups; amino groups; and halogen atoms. The aromatic hydrocarbon group may have two or more substituents, and in such cases, 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.

[0124] Specific examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, t-butylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, and t-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, unsubstituted aryl groups having 6 to 12 carbon atoms or 6 to 12 carbon atoms including substituents are preferred, unsubstituted aryl groups having 6 to 10 carbon atoms or 6 to 10 carbon atoms including substituents are more preferred, and phenyl, p-tolyl, and p-methoxyphenyl are even more preferred.

[0125] R in general formula (I-1) 1 ~R 3 The term "R" is written as 1 ~R 3 Two or more of R may be bonded to each other to form a cyclic structure. 1 ~R 3 In this case, two or three of the R 1 ~R 3Examples of the substituent include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethyleneylene, propylene, butylene, and butylene, aralkylene groups such as methylenephenylene, and arylene groups such as phenylene, naphthylene, and anthracenylene, which can bond to form a cyclic structure with a phosphorus atom. 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.

[0126] R in the above general formula (I-1) 4 ~R 7 The "organic group having 1 to 18 carbon atoms" described above is intended to include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbonoxy group, an aromatic hydrocarbonoxy group, an acyl group, a hydrocarbonoxycarbonyl group, and an acyloxy group, which have 1 to 18 carbon atoms and may be substituted or unsubstituted.

[0127] Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group include R 1 ~R 3 Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by the formula (I) include those mentioned above.

[0128] Examples of the aliphatic hydrocarbon oxy group include oxy groups having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group, such as a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, t-butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group, allyloxy group, and vinyloxy group, as well as those aliphatic hydrocarbon oxy groups which 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.

[0129] Examples of the aromatic hydrocarbon oxy group include oxy groups having a structure in which an oxygen atom is bonded to the above-mentioned aromatic hydrocarbon group, such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, or a phenoxyphenoxy group, and these aromatic hydrocarbon oxy 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.

[0130] Examples of the acyl group include aliphatic hydrocarbon carbonyl groups such as formyl, acetyl, ethylcarbonyl, butyryl, cyclohexylcarbonyl, and allylcarbonyl; aromatic hydrocarbon carbonyl groups such as phenylcarbonyl and methylphenylcarbonyl; and these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups which 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.

[0131] Examples of the hydrocarbon oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an allyloxycarbonyl group, and a cyclohexyloxycarbonyl group; aromatic hydrocarbon oxycarbonyl groups such as a phenoxycarbonyl group and a methylphenoxycarbonyl group; and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups which 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.

[0132] Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group, and a cyclohexylcarbonyloxy group; aromatic hydrocarbon carbonyloxy groups such as a phenylcarbonyloxy group and a methylphenylcarbonyloxy group; and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups which 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.

[0133] R in the above general formula (I-1) 4 ~R 7 The term "2 or more R 4 ~R 7 may be bonded to each other to form a cyclic structure" means that 2 to 4 R 4 ~R 7 may be bonded to form a single divalent to tetravalent organic group as a whole. 4 ~R 7 Examples of the cyclic group include substituents capable of forming a cyclic structure, such as alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethyleneylene, propylene, and butylene, aralkylene groups such as methylenephenylene, and arylene groups such as phenylene, naphthylene, and anthracenylene, as well as oxy or dioxy groups 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.

[0134] R in the above general formula (I-1) 4 ~R 7is not particularly limited. For example, it is preferable that each independently be 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 these, from the viewpoint of availability of raw materials, 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 preferred. Examples of an unsubstituted aryl group or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include a phenyl group, a p-tolyl group, a m-tolyl group, an o-tolyl group, and a p-methoxyphenyl group. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a t-butyl group, an octyl group, and a cyclohexyl group. From the viewpoint of curability, R 4 ~R 7 are all hydrogen atoms, or R 4 ~R 7 It is preferred that at least one of the groups is a hydroxyl group and the rest are all hydrogen atoms.

[0135] In the general formula (I-1), R 1 ~R 3 two or more of R are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms; 4 ~R 7 are all hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms. 1 ~R 3 are all alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and R 4 ~R 7 are all hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms.

[0136] From the viewpoint of rapid curing properties, the specific curing accelerator is preferably a compound represented by the following general formula (I-2).

[0137] [ka]

[0138] In formula (I-2), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 Two or more of R may be bonded to each other to form a cyclic structure; 4 ~R 6 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 4 ~R 6 Two or more of these may be bonded to each other to form a cyclic structure.

[0139] R in general formula (I-2) 1 ~R 6 Specific examples of R in general formula (I-1) 1 ~R 6 The specific examples and preferred ranges are the same as those of the above.

[0140] Specific examples of the specific curing accelerator include an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, 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, and an addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone.

[0141] The specific curing accelerator can be obtained, for example, as an adduct of a tertiary phosphine compound and a quinone compound. Specific examples of the tertiary 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(t-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, etc. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.

[0142] Specific examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, etc. From the viewpoints of moisture resistance and storage stability, p-benzoquinone is preferred.

[0143] The curable resin composition may contain a curing accelerator other than the phosphonium compound. Specific examples of curing accelerators other than phosphonium compounds include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the above cyclic amidine compounds; phenol novolac salts of the above cyclic amidine compounds or their derivatives; and combinations of these compounds with maleic anhydride, quinone compounds such as 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, and phenyl-1,4-benzoquinone. compounds having intramolecular polarization obtained by adding a compound having a π bond, such as a tetraphenylborate salt of DBU, a tetraphenylborate salt of DBN, a tetraphenylborate salt of 2-ethyl-4-methylimidazole, or a tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above-mentioned 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.

[0144] When the curable resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more of the total curing accelerator.

[0145] When the curable resin composition contains a curing accelerator, the amount thereof 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 components. When the amount of the curing accelerator is 0.1 part by mass or more per 100 parts by mass of the resin components, the composition tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin components, the curing speed is not too fast, and a good molded product tends to be obtained.

[0146] (Inorganic filler) The curable resin composition may contain an inorganic filler. In particular, when the curable resin composition is used as an encapsulant for a semiconductor package, it is preferable that the curable resin composition contains an inorganic filler.

[0147] The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers with flame retardant properties may also be used. Examples of inorganic fillers with flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxide, and zinc borate. Among these, fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred 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. The inorganic filler may be in the form of powder, beads formed by spheroidizing powder, or fibers.

[0148] When the curable resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, the content is preferably 30 to 90% by volume, more preferably 35 to 80% by volume, and even more preferably 40 to 70% by volume of the entire curable resin composition. When the content of the inorganic filler is 30% by volume or more of the entire curable resin composition, the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire curable resin composition, an increase in the viscosity of the curable resin composition is suppressed, and the fluidity is further improved, tending to result in better moldability.

[0149] The average particle size of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 0.2 μm to 10 μm, and more preferably 0.5 μm to 5 μm. When the volume average particle size is 0.2 μm or more, the increase in viscosity of the resin composition for mold underfill tends to be further suppressed. When the volume average particle size is 10 μm or less, the ability to fill narrow gaps tends to be further improved. The volume average particle size of the inorganic filler can be measured as the volume average particle size (D50) using a laser diffraction scattering particle size distribution analyzer.

[0150] The volume-average particle size of the inorganic filler in the curable resin composition or its cured product can be measured by known methods. For example, the inorganic filler is extracted from the curable resin composition or cured product using an organic solvent, nitric acid, aqua regia, or the like, and then thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion. Using this dispersion, the volume-average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer. Alternatively, the cured product can be embedded in a transparent epoxy resin or the like, polished, and the resulting cross-section observed using a scanning electron microscope to obtain the volume-based particle size distribution. Furthermore, the volume-average particle size of the inorganic filler can also be measured by continuously observing two-dimensional cross-sections of the cured product using an FIB (focused ion beam SEM) device or the like and performing three-dimensional structural analysis.

[0151] From the viewpoint of the flowability 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 wide.

[0152] [Various additives] In addition to the components described above, the curable resin composition may contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, and stress relaxation agents, as exemplified below. The curable resin composition may also contain various additives known in the art, as needed, in addition to the additives exemplified below.

[0153] (coupling agent) When the curable resin composition contains an inorganic filler, it may contain a coupling agent to enhance adhesion between the resin component and the inorganic filler. Examples of the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, titanium-based compounds, aluminum chelate compounds, and aluminum / zirconium-based compounds.

[0154] 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, adhesion to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, moldability of the package tends to be further improved.

[0155] (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 encapsulation, 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 provided with the element to be encapsulated. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0156] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≦ 0.5, m is a positive number)

[0157] When the curable resin composition contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component.

[0158] (Release agent) The curable resin composition may contain a release agent from the viewpoint of obtaining good mold release property with the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, examples include higher fatty acids such as carnauba wax, montanic acid, and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.

[0159] When the curable resin composition contains a release agent, the amount thereof is preferably 0.01 to 15 parts by mass, 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 part by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When the amount is 15 parts by mass or less, better adhesion tends to be obtained.

[0160] (Flame retardant) The curable resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0161] When the curable resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the 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.

[0162] (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 red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. The colorant may be used alone or in combination of two or more.

[0163] (stress reliever) The curable resin composition may contain a stress relief agent such as silicone oil or silicone rubber particles. By including a stress relief agent, package warpage and package cracking can be further reduced. Examples of the stress relief agent include commonly used known stress relief agents (flexibilizers). Specific examples include thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), 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 relief agents may be used alone or in combination of two or more. Among these, silicone-based stress relief agents are preferred. Examples of silicone-based stress relief agents include those having epoxy groups, those having amino groups, and polyether-modified versions of these.

[0164] (Method for preparing curable resin composition) The method for preparing the curable resin composition is not particularly limited. A common method includes thoroughly mixing predetermined amounts of components using a mixer or the like, melt-kneading the mixture using a mixing roll, extruder, or the like, cooling, and pulverizing the mixture. More specifically, for example, a method includes uniformly stirring and mixing predetermined amounts of the components described above, kneading the mixture using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, cooling, and pulverizing the mixture.

[0165] The curable resin composition is preferably solid at room temperature and normal pressure (for example, 25°C, atmospheric pressure). When the curable resin composition is solid, its shape is not particularly limited, and examples include powder, granules, tablets, etc. When the curable resin composition is in tablet form, it is preferable that the dimensions and mass of the tablet-shaped curable resin composition be such that they are suitable for the molding conditions of the package, from the viewpoint of handleability.

[0166] <Electronic component equipment> An electronic component device according to one embodiment of the present disclosure includes an element and a cured product of the above-described curable resin composition that encapsulates the element. Examples of electronic component devices include devices obtained by mounting elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and then sealing the resulting element portion with a curable resin composition. More specifically, typical resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) have a structure in which an element is fixed on a lead frame, and terminal portions of the element such as bonding pads and lead portions are connected by wire bonding, bumps, or the like, and then sealed using a curable resin composition by transfer molding or the like; TCP (Tape Carrier Package) has a structure in which an element connected to a tape carrier by bumps is sealed with a curable resin composition; and COB (Chip On Board) has a structure in which an element connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like, is sealed with a curable resin composition. Examples of such devices include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package), which have a structure in which elements are mounted on the surface of a support member having terminals for connecting a wiring board formed on the back surface thereof, the elements are connected to wiring formed on the support member by bump or wire bonding, and then the elements are sealed with a curable resin composition. The curable resin composition can also be suitably used in printed wiring boards.

[0167] Methods for encapsulating electronic component devices using a curable resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is the most common. [Example]

[0168] The above-described embodiment will be specifically described below using examples, but the scope of the above-described embodiment is not limited to these examples.

[0169] [Preparation of Curable Resin Composition] The 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 performing roll kneading under conditions of a kneading temperature of 80°C and a kneading time of 15 minutes.

[0170] (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 Corporation, product name "YX-4000H") Epoxy resin 2: Styrene-modified phenol novolac epoxy resin with an epoxy equivalent of 282 g / eq and a softening point of 59°C (Nippon Steel Sumikin Chemical Co., Ltd., product name "YDAN-1000-10C") Epoxy resin 3: Methoxynaphthalene-cresol-formaldehyde co-condensation epoxy resin with an epoxy equivalent of 250 g / eq and a softening point of 58°C (DIC Corporation, product name "HP-5000") Epoxy resin 4: Biphenylene skeleton-containing aralkyl epoxy resin with an epoxy equivalent of 282 g / eq and a softening point of 56°C (Nippon Kayaku Co., Ltd., product name "NC-3000")

[0171] (Curing agent of comparative example) Curing agent A: Phenol aralkyl resin with a hydroxyl equivalent of 176 g / eq and a softening point of 70°C (Meiwa Kasei Co., Ltd., product name "MEH-7800") Curing agent B: Biphenyl skeleton type phenol aralkyl resin with a hydroxyl group equivalent of 199 g / eq and a softening point of 89°C (Meiwa Kasei Co., Ltd., product name "MEH-7851")

[0172] (Example Curing Agent) Specific phenolic novolac resin 1:R 2 an industrial cashew nut shell liquid which is a mixture of general formulas (1-1) to (1-3) in which (A) is an aliphatic hydrocarbon group represented by group (A), and a novolak resin having a hydroxyl equivalent of 223 g / eq and a viscosity of 19.3 Pa s at 25°C, which is obtained by polycondensation of phenol with formaldehyde (Gunei Chemical Industry Co., Ltd., product name "ELP83H"); Specific phenolic novolac resin 2:R 2 an industrial cashew nut shell liquid which is a mixture of general formulas (1-1) to (1-3) in which each represents an aliphatic hydrocarbon group represented by group (A); and a novolak resin (Gunei Chemical Industry Co., Ltd., product name "ELPC80") having a hydroxyl equivalent of 209 g / eq and a viscosity of 14.0 Pa s at 25°C, which is obtained by polycondensation of cresol and phenol with formaldehyde. Certain phenolic novolac resins 3:R 2 an industrial cashew nut shell liquid which is a mixture of general formulas (1-1) to (1-3) in which each represents an aliphatic hydrocarbon group represented by group (A); and a novolak resin (Gunei Chemical Industry Co., Ltd., product name "ELPC75") having a hydroxyl equivalent of 204 g / eq and a viscosity of 23.6 Pa s at 25°C, which is obtained by polycondensation of cresol and phenol with formaldehyde. Specific phenolic novolac resin 4:R 2 a novolak resin having a hydroxyl equivalent of 204 g / eq and a viscosity of 20.2 Pa s at 25°C (Gunei Chemical Industry Co., Ltd., product name "ELC75") obtained by polycondensation of industrial cashew nut shell liquid, which is a mixture of general formulas (1-1) to (1-3), in which each represents an aliphatic hydrocarbon group represented by group (A), and cresol with formaldehyde.

[0173] (curing accelerator) Curing accelerator: Addition 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 Corporation, product name "MA-100") (mold release agent) Carnauba wax (Cerarica NODA Co., Ltd.)

[0174] [Table 1]

[0175] [Table 2]

[0176] [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 specified, the curable resin compositions were molded using 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. If necessary, post-curing was performed at 175°C for 5 hours.

[0177] (1) Spiral flow The curable resin composition was molded under the above conditions using a spiral flow measurement mold conforming to EMMI-1-66, and the flow distance (cm) was determined.

[0178] (2) Hardness when heated The curable resin composition was molded under the above conditions into a disk having a diameter of 50 mm and a thickness of 3 mm, and immediately after molding, the Shore D hardness was measured using a Shore D hardness tester (Ueshima Seisakusho Co., Ltd., HD-1120 (Type D)).

[0179] (3) 260°C shear adhesive strength The curable resin composition was molded onto a copper alloy plate (Pd-PPF) with a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm under the above conditions, and post-cured under the same conditions. The shear adhesive strength (MPa) was then measured at a shear rate of 50 μm / s using a bond tester (Daisi Japan, Series 4000) while maintaining the temperature of the copper plate at 260°C.

[0180] (4) Water absorption rate The disk molded in (2) above was post-cured under the above conditions. The resulting disk was then left at 85°C and 60% RH for 168 hours, and the change in mass before and after leaving was measured. The water absorption rate was calculated from the measurement results using the following formula. Water absorption rate (mass%) = (mass of disc after standing - mass of disc before standing) / mass of disc before standing × 100

[0181] (5) Reflow resistance An 80-pin flat package (QFP) with external dimensions of 20 mm × 14 mm × 2 mm (lead frame material: copper alloy (Pd-PPF)) mounted with an 8 mm × 10 mm × 0.4 mm silicon chip was molded using the curable resin composition under the above conditions and post-cured under the above conditions. The resulting package was humidified at 85°C and 60% RH for 168 hours. Subsequently, a reflow process was performed at predetermined temperatures (250°C, 260°C, 270°C) for 10 seconds. The presence or absence of cracks on the exterior of the package was visually observed, and the presence or absence of delamination inside the package was observed using an ultrasonic flaw detector (HYE-FOCUS, manufactured by Hitachi Construction Machinery Co., Ltd.). Reflow resistance was evaluated by the total number of packages that exhibited either cracks or delamination out of the total number of test packages (10).

[0182] [Table 3]

[0183] [Table 4]

[0184] As shown in Tables 3 and 4, Examples 1 to 15, which contain specific phenol novolac resins 1 to 4, have improved adhesion to metal (Pd-PPF) and improved reflow resistance compared to Comparative Examples 1 to 8, which do not contain specific phenol novolac resins.

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): 【Chemistry 1】 (In 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. The phenol novolak resin is a structural unit derived from a phenol compound represented by the general formula (1): The curable resin composition according to claim 1, wherein the structural unit is selected from the group consisting of a phenol compound represented by the general formula (1-1) to a phenol compound represented by the general formula (1-3): 【Chemistry 2】 (In the general formulas (1-1) to (1-3), R ２ is R in general formula (1) ２ is synonymous with

3. 3. The curable resin composition according to claim 1, wherein the phenol novolak resin further contains a structural unit derived from a phenol compound other than the phenol compound represented by 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 a 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 component device comprising: an element; and a cured product of the curable resin composition according to any one of claims 1 to 5 that encapsulates the element.

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