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

Abstract

The present invention provides 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. The present invention provides an additive for a curable resin composition, which comprises 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.

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, electronic devices have become smaller, lighter, and more powerful, leading to higher density packaging. As a result, the mainstream of electronic device devices is shifting from conventional pin insertion type packages to surface mount type packages such as IC (Integrated Circuit) and LSI (Large Scale Integration).

[0003] Surface-mount packages have a different mounting method from conventional pin-insertion packages. That is, when attaching pins to a wiring board, in conventional pin-insertion packages, the pins are inserted into the wiring board and then soldered from the back side of the wiring board, so the package is not directly exposed to high temperatures. However, in surface-mount packages, the entire electronic component device is processed in a solder bath, reflow equipment, etc., so the package is directly exposed to the soldering temperature (reflow temperature). As a result, if the package absorbs moisture, the moisture caused by the moisture absorption expands rapidly during soldering, and the generated vapor pressure acts as a peeling stress, causing peeling between the insert such as an element or lead frame and the sealing material, which may cause package cracks, poor electrical characteristics, etc. For this reason, there is a demand for the development of a sealing material that has excellent adhesion to the insert and, by extension, excellent solder heat resistance (reflow resistance).

[0004] In order to meet the above demands, for example, the use of a silane coupling agent as a modifier for the inorganic filler contained in the sealing material has been considered. Specifically, the use of an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent (for example, see Patent Document 1) has been considered. [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 range of application of packages has expanded to include in-vehicle applications, the standard 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 capable of improving the reflow resistance of a sealing structure, and a curable resin composition and an electronic component device using the same. [Means for solving the problem]

[0007] 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 number of hydroxy groups in the hydroxybenzophenone compound is 1 or 2. <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 1 or 2 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> 13. A curable resin composition comprising the additive for a curable resin composition according to claim 12 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 device, <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 5. Effect of the Invention

[0008] According to the present invention, there are provided an additive for a curable resin composition capable of improving the reflow resistance of a sealing structure, and a curable resin composition and an electronic component device using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the embodiment for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiment. In the following embodiment, the components (including element steps, etc.) are not essential unless specifically stated. The same applies to the numerical values ​​and their ranges, and they do not limit the present invention.

[0010] In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the present disclosure, in the ranges of numerical values ​​described stepwise, the upper or lower limit value described in one range of numerical values ​​may be replaced with the upper or lower limit value of another range of numerical values ​​described stepwise. In addition, in the ranges of numerical values ​​described, the upper or lower limit value of the range of numerical values ​​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] The curable resin composition containing the specific hydroxybenzophenone compound as an additive has excellent reflow resistance of the sealing structure produced using the composition. The reason is not necessarily clear, but it is considered that, for example, 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 elastic modulus and water absorption rate near the interface between the lead frame and the cured product of the curable resin composition, thereby improving the 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 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 hydrocarbon oxy 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 any of the 2nd, 3rd, and 4th positions relative to the bonding position with the carbonyl group of the aromatic ring, but is preferably the 2nd position. The number of hydroxy groups possessed by 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 are preferred, and 2-hydroxybenzophenone to 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 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 group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is not particularly limited, but is preferably bonded to an aromatic ring to which a 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 an aromatic ring to which a 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 an aromatic ring to which a 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 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 above-mentioned additive for curable resin compositions 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 photosetting. From the viewpoint of mass production, it is preferable that it is thermosetting. The curable resin component may be one that cures by self-polymerization or one that cures by reaction with a curing agent, a crosslinking agent, or the like.

[0024] The functional group that causes a reaction of the curable resin component is not particularly limited, and examples thereof include a cyclic ether group such as an epoxy group or 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 a sealing material, a curable resin component containing a cyclic ether group is preferable, a curable resin component containing an epoxy group (epoxy resin) is more preferable, and a combination of an epoxy resin and a curing agent is even more preferable.

[0025] When the curable resin component contains an epoxy resin, the type of the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, the novolac type epoxy resins include novolac resins (phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, etc.) obtained by epoxidizing novolac 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, resorcin, 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., under an acid catalyst; triphenylmethane type epoxy resins obtained by epoxidizing triphenylmethane type phenolic resins obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc., under an acid catalyst; and novolac resins obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acid catalyst, which are epoxy resins. 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 polyvalent carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine type epoxy resins in which active hydrogen bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; 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 epoxy-modified epoxy resins in which the olefin bonds in the molecule have been epoxidized; 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 the epoxy resin 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; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Furthermore, examples of the epoxy resin 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 the 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 type 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, from the viewpoint of exhibiting the performance of the specific epoxy resin, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more, of the entire epoxy resin.

[0028] Among the specific epoxy resins, from the viewpoint of fluidity, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, or sulfur atom-containing type epoxy resins are more preferable, and from the viewpoint of heat resistance, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, or aralkyl type epoxy resins are preferable. Specific examples of preferable 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 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups. 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 The oxygen atom is substituted at the 4 and 4' positions, and the 3, 3', 5, and 5' positions are methyl groups. 8 is a hydrogen atom, YL-6121H (product 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 be the same or different. n is an average value and represents a number from 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 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups. 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 all of the above is available as a commercially available product, such as ESLV-210 (product name, Sumitomo Chemical Co., Ltd.), which is a mixture of all of the above and hydrogen atoms.

[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. n is an average value and represents a number from 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 preferable. Among the epoxy resins represented by the following general formula (IV), R 11 are all hydrogen atoms, and R 12 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups.12 YSLV-80XY (product name, Nippon Steel & Sumikin Chemical Co., Ltd.), in which R 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. n is an average value and represents a number from 0 to 10.

[0038] The sulfur-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) is included. Among the epoxy resins represented by the following general formula (V), R 13 In the above, when the oxygen atom is substituted at the 4 and 4' positions, the 3 and 3' positions are t-butyl groups, the 6 and 6' positions are methyl groups, and the remaining R 13 YSLV-120TE (product name, Nippon Steel & Sumikin Chemical Co., Ltd.), in which R 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. n is an average value and represents a number from 0 to 10.

[0041] The novolac type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac type phenolic resin. For example, an epoxy resin obtained by epoxidizing a novolac type phenolic resin such as a phenol novolac resin, a cresol novolac resin, or a naphthol novolac resin using a method such as glycidyl etherification is preferred, and an epoxy resin represented by the following general formula (VI) is 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, which are cresol novolac epoxy resins, ESCN-190 and ESCN-195 (product names, Sumitomo Chemical Co., Ltd.), 14 N-770 and N-775 (trade names, DIC Corporation), which are phenol novolac epoxy resins in which all of R 14 are all hydrogen atoms, the part where i = 0 and the part where i = 1, R 15 YDAN-1000-10C (product name, Nippon Steel & Sumikin Chemical Co., Ltd.), which is a styrene-modified phenol novolac type epoxy resin having a portion where R is -CH(CH3)-Ph; 14 are all hydrogen atoms, i=1, and R 15 is a methyl group and i=2, R 15 One of the moieties is a methyl group and the other is a benzyl group. A benzyl group-modified cresol novolac epoxy resin, such as HP-5600 (trade name, DIC Corporation), is available commercially.

[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 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 preferable. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) where i=0 is available as a commercially available product.

[0045] [ka]

[0046] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and may 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 type 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 etherification of a triphenylmethane type phenolic resin such as a novolac type phenolic resin made of 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, product name), EPPN-502H (Nippon Kayaku Co., Ltd., product name), etc., in which i is 0 and k is 0, are commercially available.

[0048] [ka]

[0049] In formula (VIII), R 17 and R 18 represents a monovalent organic group having 1 to 18 carbon atoms, and may 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 etherification of a novolac type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferred, and an epoxy resin represented by the following general formula (IX) is more preferred. 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 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, and each k is independently an integer of 0 to 4. Each l and m is an average value and a number of 0 to 10, and (l+m) is a number of 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either one of the following formulas (IX-1) or (IX-2). 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 21has 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 a random copolymer containing l constitutional units and m constitutional units randomly, an alternating copolymer containing them alternately, a copolymer containing them regularly, a block copolymer containing them in a block form, etc. Any one of these may be used alone, or two or more may be used in combination.

[0055] As the copolymerized epoxy resin, Epiclon HP-5000 (trade name, DIC Corporation), which is a methoxynaphthalene-cresol formaldehyde co-condensation epoxy resin containing the following two structural units in a random, alternating or block order, and is represented by the following general formula: In the following general formula, n and m are each an average value and a number from 0 to 10, and (n+m) is a number from 0 to 10, preferably n and m are each an average value and a number from 1 to 9, and (n+m) is a number from 2 to 10.

[0056] [ka]

[0057] The aralkyl type epoxy resin is not particularly limited as long as it is an epoxy resin made from at least one selected from the group consisting of phenolic compounds such as phenol, cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and a phenolic resin synthesized from dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, an epoxy resin obtained by glycidyl etherification of a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol, cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof is preferred, and an epoxy resin represented by the following general formulas (X) and (XI) is more preferred.

[0058] Among the epoxy resins represented by the following general formula (X), 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 (product name, Nippon Kayaku Co., Ltd.), which is a mixture of epoxy resins in which i is a hydrogen atom and epoxy resins in which j 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 (product 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 formulae (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 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 1 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 With respect to the above, the term "may all 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 each element in the formula 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 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 above general formulas (II) to (XI), n is an average value, and each is preferably independently 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 decreases, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting elements and leads), etc. tends to be suppressed. It is more preferable to set n 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 viewpoints 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] From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the content of the curable resin in the curable resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass.

[0066] (hardening agent) The curable resin composition may contain a curing agent as a curable resin component. The type of the curing agent is not particularly limited and can be selected depending on the type of the 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 the phenol curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule.Specific examples of the phenol curing agent include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol, etc.; novolac-type phenol 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, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc., under an acid catalyst; and polyhydric phenol compounds such as dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. Examples of the phenol curing agent include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from the above, 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 and 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 acid 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 the phenolic hardeners, 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, copolymer type phenolic resins of benzaldehyde type phenolic resins and aralkyl type phenolic resins, and novolac type phenolic resins (these are referred to as "specific phenolic hardeners"). The specific phenolic hardeners may be used alone or in combination of two or more.

[0069] When the curing agent contains a specific phenol curing agent, from the viewpoint of fully exerting its performance, the content of the specific phenol curing agent is preferably 30 mass % or more, and more preferably 50 mass % or more, of the entire curing agent.

[0070] Examples of the aralkyl type phenolic resin include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl, etc. The aralkyl type phenolic resin may be further copolymerized with other phenolic resins. Examples of the copolymerized aralkyl type phenolic resin include a copolymerized phenolic resin of a benzaldehyde type phenolic resin and an aralkyl type phenolic resin, a copolymerized phenolic resin of a salicylaldehyde type phenolic resin and an aralkyl type phenolic resin, and a copolymerized phenolic resin of a novolac type phenolic resin and an aralkyl type phenolic resin.

[0071] The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one selected from the group consisting of phenolic 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 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 above 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 above general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., product name), MEH-7800 (Meiwa Chemical Industry Co., Ltd., product name), etc., in which i is 0 and k is 0, are commercially available.

[0076] Among the phenolic resins represented by the above 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 (product 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 preferable. 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 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 preferable.

[0081] Among the phenol resins represented by the following general formula (XVI), MEH-7500 (product name, Meiwa Kasei Co., Ltd.), in which i is 0 and k is 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 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 benzaldehyde type phenolic resin and aralkyl type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of phenolic resin obtained from a compound having a benzaldehyde skeleton and aralkyl type phenolic resin. For example, a phenolic resin represented by the following general formula (XVII) is preferable.

[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 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 type 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 phenolic compounds and naphthol compounds with an aldehyde compound under 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), i is 0 and R 35 are commercially available products such as Tamanol 758 and 759 (trade names, Arakawa Chemical Industries, Ltd.) and HP-850N (trade name, Hitachi Chemical Co., Ltd.), in which all are hydrogen atoms.

[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 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 description of "may be the same or different" means, for example, that i R 22 This means that all of the R's may be the same or different from each other. 23 ~R 36 In addition, the numbers of each of the groups in the formula may all 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 be the same or different.

[0093] In the above 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 is not too high, and the viscosity of the curable resin composition during melt molding is also low, making it difficult for unfilled defects and deformation of bonding wires (gold wires connecting elements and leads) to 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. 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 viewpoints 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 of the curable resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (number of functional groups in the curing agent / number of functional groups in the curing resin) is not particularly limited. In terms of keeping the amount of unreacted components low, it is preferably set in the range of 0.5 to 2.0, and more preferably set 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] (Cure 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 the curable resin, the desired properties of the curable resin composition, and the like.

[0098] From the viewpoint of curability and flowability, the curing accelerator preferably contains a phosphonium compound.Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl / alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, triarylphenyl ... compounds having intramolecular polarization obtained by adding a tertiary phosphine such as arylphosphine, 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 a compound having a π bond, such as 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 such a compound include compounds having intramolecular polarization obtained by reacting a halogenated phenol compound such as 4-bromo-4'-hydroxybiphenyl or 4-bromo-4'-hydroxybiphenyl with a process of dehydrohalogenation; tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetra-substituted phosphonium compounds and tetra-substituted borates having no phenyl group bonded to a boron atom such as tetra-p-tolylborate, salts of tetra-substituted phosphonium compounds with an anion obtained by removing a proton from a phenol compound, and salts of tetra-substituted phosphonium compounds with an anion 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 preferable.

[0100] [ka]

[0101] In formula (I-1), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms; 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; 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 the linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, allyl, and vinyl groups. The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl, amino, and halogen atoms. The linear or branched aliphatic hydrocarbon group may have two or more substituents, and in this case, 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, an unsubstituted alkyl group is preferable, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable, and an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and an n-octyl group are further preferable.

[0106] Specific examples of the alicyclic hydrocarbon having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups. 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 groups, alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy groups, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amino groups, and halogen atoms. The alicyclic hydrocarbon group may have two or more substituents, and in this case, 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, an unsubstituted cycloalkyl group is preferable, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group, a cyclopentyl group, and a cycloheptyl group are further preferable.

[0107] The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, butyl, and t-butyl groups, alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy groups, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amino groups, and halogen atoms. The aromatic hydrocarbon group may have two or more substituents, and in this case, 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 flowability, unsubstituted aryl groups having 6 to 12 carbon atoms or 6 to 12 carbon atoms including the substituent are preferred, unsubstituted aryl groups having 6 to 10 carbon atoms or 6 to 10 carbon atoms including the substituent 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 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 groups are bonded together to form a divalent or trivalent hydrocarbon group. 1 ~R 3Examples of the substituents include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethyleneylene, propyleneylene, and butyleneylene, aralkylene groups such as methylenephenylene, and arylene groups such as phenylene, naphthylene, and anthracenylene, which can form a cyclic structure when bonded to 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 meant 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 the 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 groups, 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, and these aliphatic hydrocarbon oxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

[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 groups, such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and 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 a formyl group, an acetyl group, an ethylcarbonyl group, a butyryl group, a cyclohexylcarbonyl group, and an allylcarbonyl group; aromatic hydrocarbon carbonyl groups such as a phenylcarbonyl group and a methylphenylcarbonyl group; 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 divalent to tetravalent organic group as a whole. 4 ~R 7 Examples of the substituent include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethyleneylene, propyleneylene, and butyleneylene, aralkylene groups such as methylenephenylene, and arylene groups such as phenylene, naphthylene, and anthracenylene, which can form a cyclic structure, and 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 them, 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 preferable. Examples of the aryl group unsubstituted 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 the linear or cyclic alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a 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 these 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. More preferably, R 1 ~R 3 all 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.

[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; 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; 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 the formula (I-1) are R 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 third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylphenyl)phosphine, tris(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 hardening 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 cyclic amidine compounds, phenol novolac salts of the 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, or 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, or 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 mass% or more of the total curing accelerator, more preferably 50 mass% or more, and even more preferably 70 mass% or more.

[0129] When the curable resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component. When the amount of the curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the resin component, 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 component, 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 a sealing material 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. Specifically, 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 can be mentioned. Inorganic fillers having a flame retardant effect may be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. Among them, fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. The inorganic fillers may be used alone or in combination of two or more. Examples of the state of the inorganic filler include powder, beads obtained by sphering powder, and fibers.

[0132] When the curable resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume of the entire curable resin composition, more preferably 35% by volume to 80% by volume, and even more preferably 40% by volume to 70% by volume. When the content of the inorganic filler is 30% by volume or more of the entire curable resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire curable resin composition, the increase in viscosity of the curable resin composition is suppressed, and the fluidity is further improved, tending to improve moldability.

[0133] The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 10 μm, and more preferably 0.5 μm to 5 μm. When the volume average particle diameter is 0.2 μm or more, the increase in viscosity of the resin composition for mold underfill tends to be more suppressed. When the volume average particle diameter is 10 μm or less, the filling ability into narrow gaps tends to be more improved. The volume average particle diameter of the inorganic filler can be measured as the volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.

[0134] The volume average particle size of the inorganic filler in the curable resin composition or the cured product thereof can be measured by a known method. For example, the inorganic filler is extracted from the curable resin composition or the cured product using an organic solvent, nitric acid, aqua regia, etc., and 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 by a laser diffraction scattering particle size distribution measuring device. Alternatively, the volume average particle size of the inorganic filler can be measured from the volume-based particle size distribution obtained by embedding the cured product in a transparent epoxy resin or the like and polishing the cross section obtained by observing the cross section with a scanning electron microscope. Furthermore, the volume average particle size of the inorganic filler can be measured by continuously observing the two-dimensional cross section of the cured product using an FIB device (focused ion beam SEM) or the like and performing three-dimensional structural analysis.

[0135] From the viewpoint of 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 distributed over a wide range.

[0136] [Various additives] In addition to the above-mentioned components, the curable resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, and a stress relaxation agent, as exemplified below. The curable resin composition may contain various additives known in the art, as necessary, 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 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 2.5 parts by mass, relative to 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more relative to 100 parts by mass of the inorganic filler, the adhesion to the frame tends to be improved. When the amount of the coupling agent is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, the moldability of the package tends to be 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 preferably contained an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be encapsulated. The ion exchanger is not particularly limited, and a conventionally known one can be used. Specifically, examples thereof 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 part by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass with respect to 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 releasability from the mold during molding. The release agent is not particularly limited, and a conventionally known one can be used. Specifically, examples thereof 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 is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the resin component. When the amount of the release agent is 0.01 parts by mass or more based on 100 parts by mass of the resin component, sufficient releasability tends 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 a conventionally known one may be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. The flame retardant may be used alone or in combination of two or more.

[0145] When the curable resin composition contains a flame retardant, the amount 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. The colorant may be used alone or in combination of two or more.

[0147] (Stress reliever) The curable resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By containing a stress relaxation agent, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include known stress relaxation agents (flexible agents) that are generally used. Specifically, examples of the stress relaxation agent 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 relaxation agent may be used alone or in combination of two or more. Among them, silicone-based stress relaxation agents are preferred. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, and those modified with polyether.

[0148] (Method for preparing curable resin composition) The method for preparing the curable resin composition is not particularly limited. A general method includes a method in which a predetermined amount of components is thoroughly mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder, or the like, cooled, and pulverized. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like that has been heated to 70°C to 140°C in advance, cooled, and pulverized can be mentioned.

[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, the shape is not particularly limited, and examples thereof include powder, granules, tablets, etc. When the curable resin composition is in tablet form, the dimensions and mass are preferably set to be suitable for the molding conditions of the package from the viewpoint of handling.

[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, terminal parts of the element such as bonding pads and lead parts are connected by wire bonding, bumps, or the like, and then sealed by transfer molding or the like using a curable resin composition; 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 a module include a BGA (Ball Grid Array), a CSP (Chip Size Package), and an MCP (Multi Chip Package), which have a structure in which an element is mounted on the surface of a support member having terminals for connecting a wiring board formed on the back side thereof, the element is connected to wiring formed on the support member by bump or wire bonding, and then the element is sealed with a curable resin composition. The curable resin composition can also be suitably used in printed wiring boards.

[0151] Methods for encapsulating electronic device components using a curable resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Of these, low-pressure transfer molding is the most common. EXAMPLES

[0152] The above embodiment will be specifically described below using examples, but the scope of the above 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 type 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 type 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 type 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 type epoxy resin with an epoxy equivalent of 197 g / eq (Chang Chun Plastics Co., Ltd., product name "CNE-195LLB")

[0155] (hardening agent) Hardener 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") Hardener 2: Biphenyl skeleton type phenol aralkyl resin with hydroxyl equivalent of 199 g / eq and softening point of 89°C (Meiwa Kasei Co., Ltd., product name "MEH-7851") Hardener 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., product name "Kemisorb12") Hydroxybenzophenone compound A: 2,4-dihydroxybenzophenone (Chemipro Chemical Co., Ltd., product name "Kemisorb10") Hydroxybenzophenone compound B: 2-hydroxy-4-methoxybenzophenone (Chemipro Chemical Co., Ltd., product name "Kemisorb11") Hydroxybenzophenone compound C: 2,2′-dihydroxy-4-methoxybenzophenone (Chemipro Chemical Co., Ltd., product name "Kemisorb 111")

[0157] (Cure accelerator) Curing accelerator: Addition product of triphenylphosphine and 1,4-benzoquinone (Inorganic filler) Spherical fused silica (volume average particle size 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") (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 (HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.).

[0163] (3) Water absorption rate The disk molded in (2) above was post-cured under the above conditions. The disk was then left for 168 hours under conditions of 85°C and 60% RH, and the mass change 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 disk after standing - mass of disk before standing) / mass of disk before standing × 100

[0164] (4) Reflow resistance An 80-pin flat package (QFP) with external dimensions of 20 mm x 14 mm x 2 mm (lead frame material: copper alloy, die pad upper surface and lead tip silver-plated product) equipped with a silicon chip of 8 mm x 10 mm x 0.4 mm was molded using the curable resin composition under the above conditions and post-cured under the above conditions. The obtained package was humidified under conditions of 85 ° C and 85% RH for 168 hours. Thereafter, reflow treatment was performed under conditions of a predetermined temperature (250 ° C, 260 ° C, 270 ° C) and 10 seconds, and the presence or absence of cracks on the outside of the package was visually observed, and the presence or absence of peeling inside the package was observed with an ultrasonic flaw detector (HYE-FOCUS, manufactured by Hitachi Construction Machinery Co., Ltd.). Reflow resistance was evaluated by the total number of packages in which either cracks or peeling occurred out of the 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 specific hydroxybenzophenone compounds, did not show a significant improvement in reflow resistance compared to Example 2, which has 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 hydrocarbonoxy group having 6 to 12 carbon atoms, The curable resin composition includes an epoxy resin and a curing agent. The epoxy resin is an additive for a curable resin composition, which includes a styrene-modified phenol novolac type epoxy resin or a methoxynaphthalene-cresol formaldehyde co-condensation type epoxy 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 1 or 2 aliphatic hydrocarbon groups having 6 to 12 carbon atoms or 1 or 2 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 composition includes an epoxy resin and a curing agent. The epoxy resin is a curable resin composition containing a styrene-modified phenol novolac type epoxy resin or a methoxynaphthalene-cresol formaldehyde co-condensation type epoxy resin.

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.

Images