Additive for curable resin composition, curable resin composition and electronic component device

Abstract

To provide an additive for curable resin composition that can improve reflow resistance of a sealing structure, and a curable resin composition and an electronic component device including the same.SOLUTION: An additive for curable resin composition contains a hydroxy benzophenone compound having a C6-12 aliphatic hydrocarbon group or a C6-12 aliphatic hydrocarbon oxy group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an additive for a curable resin composition, 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 has been investigated (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

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

[0006] In recent years, as the application fields of packages have expanded to include in-vehicle applications, the level of reflow resistance required of packages has also increased. In view of the above circumstances, an object of the present invention is to provide an additive for a curable resin composition that can improve the reflow resistance of a sealing structure, and a curable resin composition and an electronic component device that use the same. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments. <1> An additive for a curable resin composition, comprising a hydroxybenzophenone compound having an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms. <2> The hydroxybenzophenone compound has 1 or 2 hydroxy groups. <1> The additive for a curable resin composition according to claim 1. <3> the hydroxybenzophenone compound has 1 or 2 aliphatic hydrocarbon groups having 6 to 12 carbon atoms or aliphatic hydrocarbon oxy groups having 6 to 12 carbon atoms; <1> or <2> The additive for a curable resin composition according to claim 1. <4> <1> ~ <3> 10. A curable resin composition comprising the additive for a curable resin composition according to any one of claims 1 to 9 and a curable resin component. <5> The curable resin component includes an epoxy resin and a curing agent. <4> The curable resin composition according to claim 1. <6> For use as an encapsulant for electronic component devices, <4> or <5> The curable resin composition according to claim 1. <7> An element and a device for sealing the element <4> ~ <6> 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]

[0008] According to the present invention, there are provided an additive for a curable resin composition that can improve the reflow resistance of a sealing structure, as well as a curable resin composition and an electronic component device that use the same. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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.

[0010] 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.

[0011] <Additives for curable resin compositions> The additive for a curable resin composition of the present disclosure contains a hydroxybenzophenone compound having an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms (hereinafter also referred to as a specific hydroxybenzophenone compound).

[0012] A curable resin composition containing a specific hydroxybenzophenone compound as an additive provides a sealed structure produced therefrom with excellent reflow resistance. The reason for this is not entirely clear, but it is thought that the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms contained in the specific hydroxybenzophenone compound acts to reduce the modulus of elasticity and the water absorption rate near the interface between the lead frame and the cured product of the curable resin composition, thereby improving reflow resistance.

[0013] Furthermore, when a curable resin composition containing a specific hydroxybenzophenone compound as an additive is used as an encapsulant for a package including a lead frame whose surface is made of silver, the curable resin composition has particularly excellent reflow resistance. Therefore, the curable resin composition containing a specific hydroxybenzophenone compound as an additive is particularly suitable as an encapsulant for a package including a lead frame whose surface is made of silver.

[0014] In the present disclosure, the term "specific hydroxybenzophenone compound" refers to a compound (hydroxybenzophenone compound) having a benzophenone skeleton and a hydroxy group bonded to at least one of the two aromatic rings that form the benzophenone skeleton, and having an aliphatic hydrocarbon group or an aliphatic hydrocarbonoxy group having 6 to 12 carbon atoms.

[0015] The position of the hydroxy group in the specific hydroxybenzophenone compound is not particularly limited, and may be the 2nd, 3rd, or 4th position relative to the bonding position to the carbonyl group of the aromatic ring, but is preferably the 2nd position. The number of hydroxy groups in the specific hydroxybenzophenone compound is not particularly limited, but is preferably 1 or 2, and more preferably 1.

[0016] Specific examples of the specific hydroxybenzophenone compound include hydroxybenzophenone compounds such as 2-hydroxybenzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2,2'-dihydroxybenzophenone, 3,3'-dihydroxybenzophenone, and 4,4'-dihydroxybenzophenone, to which an aliphatic hydrocarbon group or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is bonded. Among these, 2-hydroxybenzophenone, 3-hydroxybenzophenone, and 4-hydroxybenzophenone to which an aliphatic hydrocarbon group or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is bonded is preferred, and 2-hydroxybenzophenone to which an aliphatic hydrocarbon group or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is bonded is more preferred.

[0017] The number of aliphatic hydrocarbon groups having 6 to 12 carbon atoms or aliphatic hydrocarbon oxy groups having 6 to 12 carbon atoms in the specific hydroxybenzophenone compound is not particularly limited, but is preferably 2 or less, and more preferably 1. The position of the aliphatic hydrocarbon groups having 6 to 12 carbon atoms or aliphatic hydrocarbon oxy groups having 6 to 12 carbon atoms is not particularly limited, but is preferably bonded to the aromatic ring to which the hydroxy group is bonded.

[0018] In one embodiment, the specific hydroxybenzophenone compound may have a structure in which an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is bonded to the aromatic ring to which the hydroxy group of 2-hydroxybenzophenone is bonded, or may have a structure in which an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is bonded to the fourth position of the aromatic ring to which the hydroxy group of 2-hydroxybenzophenone is bonded.

[0019] The aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms contained in the specific hydroxybenzophenone compound may have 8 to 10 carbon atoms, or may have 8 carbon atoms.

[0020] The aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms contained in the specific hydroxybenzophenone compound may or may not have an unsaturated double bond, but it is preferable that it does not have an unsaturated double bond.

[0021] The aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms contained in the specific hydroxybenzophenone compound may be branched or unbranched, but is preferably unbranched.

[0022] <Curable resin composition> The curable resin composition of the present disclosure contains the additive for curable resin compositions described above and a curable resin component.

[0023] The curable resin component is not particularly limited as long as it forms a three-dimensional crosslinked structure by reaction, and may be thermosetting or photocurable. From the viewpoint of mass production, thermosetting is preferable. The curable resin component may be one that cures by self-polymerization or one that cures by reaction with a curing agent, crosslinking agent, etc.

[0024] The functional group that causes a reaction in the curable resin component is not particularly limited, and examples thereof include cyclic ether groups such as an epoxy group and an oxetanyl group, a hydroxyl group, a carboxy group, an amino group, an acryloyl group, an isocyanate group, a maleimide group, an alkenyl group, etc. From the viewpoint of the balance of properties as an encapsulant, a curable resin component containing a cyclic ether group is preferred, a curable resin component containing an epoxy group (epoxy resin) is more preferred, and a combination of an epoxy resin and a curing agent is even more preferred.

[0025] When the curable resin component contains an epoxy resin, the type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, the novolac type epoxy resins include novolac type epoxy resins (phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, etc.) obtained by epoxidizing novolac resins obtained by condensing or co-condensing, under an acid 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 type epoxy resins obtained by epoxidizing triphenylmethane type phenolic resins obtained by condensing or co-condensing, under an acid catalyst, the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc.; and novolac type epoxy resins obtained by co-condensing, under an acid catalyst, the above phenolic compound and naphthol compound with an aldehyde compound, Copolymerized epoxy resins, which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; diphenylmethane-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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] [ka]

[0031] 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.

[0032] 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.).

[0033] [ka]

[0034] 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.

[0035] 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.

[0036] [ka]

[0037] 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.

[0038] 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.

[0039] [ka]

[0040] 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.

[0041] 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 ESCN-190 and ESCN-195 (trade names of Sumitomo Chemical Co., Ltd.), which are cresol novolac epoxy resins where i=1, 14 are all hydrogen atoms and i=0, and N-770 and N-775 (trade names of DIC Corporation) are phenol novolac epoxy resins in which R 14 are all hydrogen atoms, and the part where i=0 and the part where i=1 are R 15 but- Styrene-modified phenolic novolac epoxy resin containing the moiety CH(CH3)-Ph YDAN-1000-10C (Nippon Steel Sumikin Chemical Co., Ltd., product name), 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), a benzyl-modified cresol novolac epoxy resin having one methyl group and one benzyl group, is commercially available.

[0042] [ka]

[0043] 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. 15represents 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.

[0044] 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.

[0045] [ka]

[0046] 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.

[0047] 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.

[0048] [ka]

[0049] In formula (VIII), R17 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.

[0050] 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.

[0051] [ka]

[0052] 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).

[0053] [ka]

[0054] 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.

[0055] 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.

[0056] [ka]

[0057] 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.

[0058] Among the epoxy resins represented by the following general formula (X), those in which i is 0 and R 38 is 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.

[0059] [ka]

[0060] 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 41represents 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.

[0061] 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.

[0062] 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.

[0063] The functional group equivalent of the curable resin (epoxy equivalent in the case of an epoxy resin) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of the curable resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

[0064] The softening point or melting point of the curable 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.

[0065] The content of the curable resin in the curable resin composition is preferably 0.5 to 50% by mass, more preferably 2 to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, etc.

[0066] (hardening agent) The curable resin composition may contain a curing agent as a curable resin component. The type of curing agent is not particularly limited and can be selected depending on the type of curable resin component, the desired properties of the curable resin composition, and the like. When the curable resin component contains an epoxy resin, examples of the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, etc. From the viewpoint of achieving 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 preferred, and from the viewpoint of electrical reliability, a phenol curing agent is more preferred.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] [ka]

[0073] 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, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each p is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0074] 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.

[0075] 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.

[0076] 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 SN-170 (trade name, Nippon Steel & Sumikin Chemical Co., Ltd.) in which j is 0, k is 1, 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.

[0077] 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.

[0078] [ka]

[0079] 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.

[0080] 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.

[0081] 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.

[0082] [ka]

[0083] 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.

[0084] 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.

[0085] 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.

[0086] [ka]

[0087] 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.

[0088] 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.

[0089] 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.).

[0090] [ka]

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] The equivalent ratio between the curable resin and 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 curable resin (number of functional groups in the curing agent / number of functional groups in the curable 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. In terms of moldability and reflow resistance, it is even more preferably set in the range of 0.8 to 1.2.

[0097] (curing accelerator) The curable resin composition may contain a curing accelerator. The type of 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.

[0098] 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.

[0099] 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.

[0100] [ka]

[0101] 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 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and R 4 ~R 7 Two or more of these may be bonded to each other to form a cyclic structure.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] From the viewpoint of rapid curing properties, the specific curing accelerator is preferably a compound represented by the following general formula (I-2).

[0121] [ka]

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] (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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] [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.

[0137] (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.

[0138] 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.

[0139] (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.

[0140] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0<X≦0.5, m is a positive number)

[0141] 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 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the resin component.

[0142] (Release agent) The curable resin composition may contain a release agent from the viewpoint of obtaining good mold release properties 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.

[0143] 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.

[0144] (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.

[0145] 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.

[0146] (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.

[0147] (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.

[0148] (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.

[0149] 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.

[0150] <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.

[0151] 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]

[0152] 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.

[0153] [Preparation of Curable Resin Composition] The curable resin compositions of Examples 1 to 12 and Comparative Examples 1 to 12 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.

[0154] (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") Epoxy resin 5: orthocresol novolac epoxy resin with an epoxy equivalent weight of 197 g / eq (Chang Chun Plastics Co., Ltd., product name "CNE-195LLB")

[0155] (hardening agent) Curing agent 1: 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 2: 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") Curing agent 3: Orthocresol novolac resin with a hydroxyl equivalent of 116 g / eq and a softening point of 64°C (Meiwa Kasei Co., Ltd., product name "MEH-5100-5S")

[0156] (Hydroxybenzophenone compounds) Hydroxybenzophenone compound 1: 2-hydroxy-4-n-octyloxybenzophenone (Chemipro Chemical Co., Ltd., trade name "Kemisorb 12") Hydroxybenzophenone compound A: 2,4-dihydroxybenzophenone (Chemipro Chemical Co., Ltd., trade name "Kemisorb 10") Hydroxybenzophenone compound B: 2-hydroxy-4-methoxybenzophenone (Chemipro Chemical Co., Ltd., trade name "Kemisorb 11") Hydroxybenzophenone compound C: 2,2′-dihydroxy-4-methoxybenzophenone (Chemipro Chemical Co., Ltd., trade name "Kemisorb 111")

[0157] (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.)

[0158] [Table 1]

[0159] [Table 2]

[0160] [Evaluation of Curable Resin Composition] The properties of the curable resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 12 were evaluated by the following property tests. The evaluation results are shown in Tables 3 and 4 below. 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.

[0161] (1) Spiral flow Using a spiral flow measurement mold conforming to EMMI-1-66, the encapsulating epoxy molding material was molded under the above conditions, and the flow distance (cm) was determined.

[0162] (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)).

[0163] (3) 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

[0164] (4) Reflow resistance An 80-pin flat package (QFP) with dimensions of 20 mm × 14 mm × 2 mm (lead frame material: copper alloy, die pad top surface and lead tips silver-plated) incorporating an 8 mm × 10 mm × 0.4 mm silicon chip was molded using the curable resin composition and post-cured under the conditions described above. The resulting packages were humidified at 85°C and 85% RH for 168 hours. Subsequently, reflow treatments were performed at predetermined temperatures (250°C, 260°C, 270°C) for 10 seconds. The presence or absence of external cracks on the package was visually observed, and the presence or absence of internal delamination on the package was observed using an ultrasonic flaw detector (HYE-FOCUS, manufactured by Hitachi Construction Machinery Co., Ltd.). Reflow resistance was evaluated by the sum of the number of packages that exhibited either cracks or delamination out of the total number of test packages (10).

[0165] [Table 3]

[0166] [Table 4]

[0167] As shown in Tables 3 and 4, Examples 1 to 12, which contained hydroxybenzophenone compound 1 corresponding to the specific hydroxybenzophenone compound, showed significantly improved reflow resistance compared to Comparative Examples 1 to 9, which did not contain a hydroxybenzophenone compound. Comparative Examples 10 to 12, which contain hydroxybenzophenone compounds A, B, and C that do not correspond to the specific hydroxybenzophenone compounds, did not show a significant improvement in reflow resistance compared to Example 2, which had the same composition except for containing hydroxybenzophenone compound 1.

Claims

1. An additive for a curable resin composition, comprising a hydroxybenzophenone compound having an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms, The curable resin composition includes an epoxy resin and a curing agent, The curing agent is an additive for a curable resin composition, which contains a biphenyl skeleton-type phenol aralkyl resin.

2. The additive for a curable resin composition according to claim 1 , wherein the hydroxybenzophenone compound has one or two hydroxy groups.

3. The additive for a curable resin composition according to claim 1 or claim 2, wherein the hydroxybenzophenone compound has one or two aliphatic hydrocarbon groups having 6 to 12 carbon atoms or one or two aliphatic hydrocarbon oxy groups having 6 to 12 carbon atoms.

4. The additive for a curable resin composition according to any one of claims 1 to 3 and a curable resin component, the curable resin component includes an epoxy resin and a curing agent; The curable resin composition contains a biphenyl skeleton-type phenol aralkyl resin as the curing agent.

5. The curable resin composition according to claim 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 claim 4 or 5 that encapsulates the element.

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