Curable resin composition and electronic component device

Abstract

The present invention provides a curable resin composition that exhibits excellent curability at low temperatures, and an electronic component device obtained using the same. [Solution] A curable resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin comprises an epoxy-containing group bonded to an aromatic ring to which an electron-donating group is not bonded, and the curing agent comprises a curing agent having a hydroxyl group bonded to an aromatic ring to which an electron-donating group is bonded.

Description

Technical Field

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

Background Art

[0002] With the miniaturization, weight reduction, and high performance of electronic devices, the density of mounting has been increasing. As a result, the mainstream of electronic component devices is changing from conventional pin insertion type packages to surface mounting type packages such as IC (Integrated Circuit) and LSI (Large Scale Integration). Furthermore, the diversification of encapsulation technologies such as SiP (System in a Package) and integrated encapsulation is progressing (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] With the diversification of encapsulation technologies, the components mounted on the chip are also diversifying, and depending on the type of component (sensor, inductor, etc.), it is assumed that they will be affected by the heat when curing the encapsulant. Therefore, it is desired to reduce the heating temperature when curing the encapsulant. In view of the above circumstances, an object of the present invention is to provide a curable resin composition excellent in curability at low temperatures, and an electronic component device obtained using the same.

Means for Solving the Problems

[0005] Means for solving the above problems include the following embodiments. <1> A curable resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin comprises an epoxy-containing group bonded to an aromatic ring to which an electron-donating group is not bonded, and the curing agent comprises a curing agent having a hydroxyl group bonded to an aromatic ring to which an electron-donating group is bonded. <2> The electron-donating group is at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, amino groups, and methoxy groups. <1> The curable resin composition described above. <3> The epoxy resin having an epoxy-containing group bonded to an aromatic ring to which the electron-donating group is not bonded has a biphenyl structure. <1> or <2> The curable resin composition described above. <4> The curing agent having a hydroxyl group bonded to the aromatic ring to which the electron-donating group is attached has a structure obtained by novolacizing the phenol compound to which the electron-donating group is attached. <1> ~ <3> A curable resin composition according to any one of the following items. <5> The curing agent having a hydroxyl group bonded to the aromatic ring to which the electron-donating group is attached has a structure obtained by novolacizing a phenol compound to which the electron-donating group is attached in the ortho position. <1> ~ <4> A curable resin composition according to any one of the following items. <6> Further comprising an imidazole compound, <1> ~ <5> A curable resin composition according to any one of the following items. <7> For use as a encapsulating material for electronic component devices, <1> ~ <6> A curable resin composition according to any one of the following items. <8> An element and a seal for the element. <1> ~ <7> An electronic component device comprising a cured product of a curable resin composition according to any one of the items. [Effects of the Invention]

[0006] According to the present invention, a curable resin composition exhibiting excellent curability at low temperatures, and an electronic component device obtained using the same are provided. [Modes for carrying out the invention]

[0007] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit the present invention.

[0008] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this disclosure, the content or amount of each component in a composition means the total content or amount of the multiple substances present in the composition, unless otherwise specified, if multiple substances corresponding to each component are present in the composition. In this disclosure, if there are multiple types of particles corresponding to each component in the composition, the particle size refers to the value for a mixture of such multiple types of particles present in the composition, unless otherwise specified.

[0009] <Curable resin composition> The curable resin composition of this disclosure comprises an epoxy resin and a curing agent, wherein the epoxy resin comprises an epoxy resin having an epoxy-containing group bonded to an aromatic ring to which an electron-donating group is not bonded (hereinafter also referred to as a specific epoxy resin), and the curing agent comprises a curing agent having a hydroxyl group bonded to an aromatic ring to which an electron-donating group is bonded (hereinafter also referred to as a specific curing agent).

[0010] The curable resin composition having the above configuration exhibits excellent curability at low temperatures (e.g., 150°C or below). Although the reason for this is not entirely clear, it is thought that the reaction between the epoxy-containing group bonded to the aromatic ring without an electron-donating group and the hydroxyl group bonded to the aromatic ring with an electron-donating group improves the reactivity between the epoxy resin and the curing agent, thereby promoting curing at low temperatures.

[0011] The curable resin composition of this disclosure exhibits superior curability at lower temperatures compared to conventional curable resin compositions, and is therefore useful, for example, as a encapsulant for electronic component devices containing components with poor heat resistance. Furthermore, it is expected to reduce substrate warping by suppressing thermal shrinkage during curing.

[0012] In this disclosure, "electron-donating group" means a substituent that has the property of enhancing the activity of the aromatic ring to which it is attached, and its type is not particularly limited. Examples include alkyl groups having 1 to 6 carbon atoms, amino groups, methoxy groups, etc. In this disclosure, epoxy-containing groups or hydroxyl groups are not included in the definition of "electron-donating groups." Furthermore, if the epoxy resin or curing agent is a polymer, the structure corresponding to the main chain is not included in the substituents.

[0013] In this disclosure, "epoxy-containing group" means a substituent containing an epoxy group (ethylene oxide structure). Specifically, this includes epoxy groups directly bonded to an aromatic ring, and epoxy groups bonded to an aromatic ring via a C1-C3 hydrocarbon group (preferably a methylene group), a C1-C3 hydrocarbon oxy group (preferably a methylene oxy group), or a C1-C3 hydrocarbon amino group.

[0014] In this disclosure, "aromatic rings to which epoxy-containing groups are bonded" include benzene rings and fused rings of two or more benzene rings (such as naphthalene). In the case of structures in which two or more benzene rings are linked by single bonds, etc. (such as biphenyl structures), the benzene ring to which the epoxy-containing group is directly bonded is considered the aromatic ring to which the epoxy-containing group is bonded.

[0015] (Epoxy resin) The epoxy resin included in the curable resin composition is not particularly limited as long as it contains a specific epoxy resin, and can be selected according to the desired properties of the curable resin composition. A specific epoxy resin may have only epoxy-containing groups bonded to aromatic rings that do not have electron-donating groups attached, or it may have epoxy-containing groups bonded to aromatic rings that do not have electron-donating groups attached, and epoxy-containing groups bonded to aromatic rings that do have electron-donating groups attached.

[0016] From the viewpoint of curing properties at low temperatures, the proportion of the specific epoxy resin in the epoxy resin is preferably 20% by mass or more of the total epoxy resin, and more preferably 30% by mass or more. There is no particular upper limit to the proportion of the specific epoxy resin in the epoxy resin. From the viewpoint of balancing the properties of the cured product, the proportion of the specific epoxy resin in the epoxy resin may be 90% by mass or less of the total epoxy resin, or 80% by mass or less.

[0017] From the viewpoint of reactivity at low temperatures, the specific epoxy resin preferably has a structure in which two aromatic rings are linked by a single bond or a divalent linking group, more preferably has a structure in which two aromatic rings are linked by a single bond (biphenyl structure), and even more preferably has a structure represented by the following general formula (A) as the biphenyl structure. The specific epoxy resin having a biphenyl structure may further have structures other than the biphenyl structure (such as a triphenylmethane structure).

[0018] [ka]

[0019] In general formula (A), * represents a bond position with an adjacent atom, and at least one of the * represents a bond position with an epoxy-containing group.

[0020] Specifically, the epoxy resins include: novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing a novolac resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing a novolac resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound (benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst; triphenylmethane-type epoxy resins obtained by condensing or co-condensing a triphenylmethane-type phenolic resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound (benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst; and novolac resins obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst. Copolymer epoxy resins that are epoxidized from; diphenylmethane type epoxy resins that are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers of bisphenol S, etc.; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins that are glycidyl esters of polycarboxylic acid compounds 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 replaced with a glycidyl group; dicyclopentadiene type epoxy resins that are epoxidized from a copolymer resin of dicyclopentadiene and a phenol compound;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 have epoxidized olefin bonds within the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenol resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenol resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenol resins; and dicyclopentadiene-modified phenol resins, which are glycidyl ethers of dicyclo Examples of 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, which are epoxidized aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Furthermore, epoxides of silicone resins and acrylic resins can also be cited as epoxy resins. These epoxy resins may be used individually or in combination of two or more types.

[0021] From the viewpoint of balancing 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 are preferred as epoxy resins.

[0022] Specific examples of the biphenyl type epoxy resin include epoxy resins represented by the following general formula (II). Among the epoxy resins represented by the following general formula (II), when the positions where oxygen atoms are substituted among Rs 8 are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups, and the other Rs 8 are hydrogen atoms, YX-4000H (trade name, Mitsubishi Chemical Corporation), all Rs 8 are hydrogen atoms, 4,4'-bis(2,3-epoxypropoxy)biphenyl, when all Rs 8 are hydrogen atoms and in the case where all Rs 8 are hydrogen atoms and when the positions where oxygen atoms are substituted among Rs 8 are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups and the other Rs are hydrogen atoms, a mixture such as YL-6121H (trade name, Mitsubishi Chemical Corporation) are commercially available.

[0023]

Chemical formula

[0024] In formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms (in the case of a specific epoxy resin, preferably a hydrogen atom), and they may all be the same or different from each other. n is an average value and represents a number from 0 to 10.

[0025] Specific examples of the stilbene type epoxy resin include epoxy resins represented by the following general formula (III).

[0026]

Chemical formula

[0027] In formula (III), R 9 and R 10represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms (in the case of a specific epoxy resin, preferably a hydrogen atom), and each of these may be the same or different. n is an average value and represents a number between 0 and 10.

[0028] Specific examples of diphenylmethane type epoxy resins include epoxy resins represented by the following general formula (IV). Among the epoxy resins represented by the following general formula (IV), R 11 All of them are hydrogen atoms, R 12 Of these, when the positions where the oxygen atom is substituted are designated as positions 4 and 4', the positions 3, 3', 5, and 5' are methyl groups, and the other R 12 Products such as YSLV-80XY (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name), which contains a hydrogen atom, are available commercially.

[0029] [ka]

[0030] In formula (IV), R 11 R is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. 12 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms (in the case of a specific epoxy resin, preferably a hydrogen atom), and each of these may be the same or different. n is an average value and represents a number between 0 and 10.

[0031] Specific examples of sulfur atom-containing epoxy resins include epoxy resins represented by the following general formula (V). Among the epoxy resins represented by the following general formula (V), R 13 Of these, when the positions where the oxygen atom is substituted are defined as positions 4 and 4', the 3,3' positions are t-butyl groups, the 6,6' positions are methyl groups, and the other R 13 Products such as YSLV-120TE (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name), which contains a hydrogen atom, are available commercially.

[0032] [ka]

[0033] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms (in the case of a specific epoxy resin, preferably a hydrogen atom), and each of these may be the same or different. n is an average value and represents a number between 0 and 10.

[0034] Specific examples of novolac-type epoxy resins include epoxy resins represented by the following general formula (VI). Among the epoxy resins represented by the following general formula (VI), R 14 All of them are hydrogen atoms, R 15 The methyl group is i=1 in ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd., product name), R 14 All of them are hydrogen atoms, i=0, N-770, N-775 (DIC Corporation, product name), R 14 All of them are hydrogen atoms, with parts where i=0 and parts where i=1, R 15 YDAN-1000-10C (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name), R is a styrene-modified phenol novolac type epoxy resin having a moiety of -CH(CH3)-Ph. 14 All of them are hydrogen atoms, i=1, R 15 The part where i is a methyl group is i=2, and R 15 HP-5600 (DIC Corporation, trade name), a benzyl group-modified cresol novolac type epoxy resin having a portion where one is a methyl group and the other is a benzyl group, is available commercially.

[0035] [ka]

[0036] In formula (VI), R 14 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms (preferably a hydrogen atom), and each of them may be the same or different. 15represents a monovalent organic group having 1 to 18 carbon atoms, and each may be identical or different. Each i independently represents an integer from 0 to 3 (preferably 0 in the case of a specific epoxy resin). n is the average value and represents a number from 0 to 10.

[0037] A specific example of a dicyclopentadiene-type epoxy resin is the epoxy resin represented by the following general formula (VII). Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name), where i=0, is available commercially.

[0038] [ka]

[0039] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and each may be identical or different. Each i independently represents an integer from 0 to 3 (preferably 0 in the case of a specific epoxy resin). n is the average value and represents a number from 0 to 10.

[0040] Specific examples of triphenylmethane-type epoxy resins include epoxy resins represented by the following general formula (VIII). 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), where i is 0 and k is 0, are commercially available.

[0041] [ka]

[0042] In formula (VIII), R 17 and R 18represents a monovalent organic group having 1 to 18 carbon atoms, and each group may be identical or different. Each i is an independent integer from 0 to 3 (preferably 0 in the case of a specific epoxy resin), and each k is an independent integer from 0 to 4 (preferably 0 in the case of a specific epoxy resin). n is the average value and represents a number from 0 to 10.

[0043] A specific example of a copolymer epoxy resin obtained by epoxidizing a novolac resin obtained from naphthol compounds, phenol compounds, and aldehyde compounds is the epoxy resin represented by the following general formula (IX). Among the epoxy resins represented by the following general formula (IX), R 21 Products such as NC-7300 (Nippon Kayaku Co., Ltd., trade name), in which the group is a methyl group with i = 1, j = 0, and k = 0, are commercially available.

[0044] [ka]

[0045] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i is an integer from 0 to 3 (preferably 0 in the case of a specific epoxy resin), j is an integer from 0 to 2 (preferably 0 in the case of a specific epoxy resin), and k is an integer from 0 to 4 (preferably 0 in the case of a specific epoxy resin). l and m are average values, numbers from 0 to 10, and (l+m) is a number from 0 to 10. The end 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 equation (IX). 19 ~R 21 The definitions of i, j, and k are the same. n is either 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).

[0046] [ka]

[0047] Examples of epoxy resins represented by the above general formula (IX) include random copolymers containing l constituent units and m constituent units randomly, alternating copolymers containing units alternately, copolymers containing units regularly, and block copolymers containing units in a block-like manner. Any one of these may be used alone, or two or more may be used in combination.

[0048] Specific examples of aralkyl epoxy resins include epoxy resins represented by the following general formulas (X) and (XI). Among the epoxy resins represented by the following general formula (X), i is 0 and R 38 NC-3000L (Nippon Kayaku Co., Ltd., product name) has a hydrogen atom, i is 0, and R 38 Epoxy resins in which hydrogen atoms and all R of general formula (II) 8 Epoxy resins in which i is a hydrogen atom are mixed in a mass ratio of 80:20, such as CER-3000 (Nippon Kayaku Co., Ltd., trade name), are commercially available. In addition, among epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name), in which i is 0, j is 0, and k is 0, are commercially available.

[0049] [ka]

[0050] In equations (X) and (XI), R 38 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. 37 , R 39 ~R 41represents a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. Each i is an independent integer from 0 to 3 (preferably 0 in the case of a specific epoxy resin), each j is an independent integer from 0 to 2 (preferably 0 in the case of a specific epoxy resin), each k is an independent integer from 0 to 4 (preferably 0 in the case of a specific epoxy resin), and each l is an independent integer from 0 to 6 (preferably 0 in the case of a specific epoxy resin). n is the average value, and each is an independent number from 0 to 10.

[0051] In the above general formulas (II) to (XI), R 8 ~R 21 and R 37 ~R 41 Regarding this, "they may all be the same or all different" means, for example, the 8 to 88 R in equation (II) 8 This means that all of them may be the same or different. 9 ~R 21 and R 37 ~R 41 Regarding this as well, it means that the number of each element included in the formula may all be the same or different. Also, R 8 ~R 21 and R 37 ~R 41 These can be the same or different. For example, R 9 and R 10 All of them may be the same or different. Furthermore, the organic group having 1 to 18 carbon atoms in general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

[0052] In the above general formulas (II) to (XI), n is an average value, and it is preferable that each is 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, the viscosity of the curable resin composition during melt molding decreases, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting the element and lead) tends to be suppressed. It is more preferable that n be set in the range of 0 to 4.

[0053] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

[0054] When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of ease of handling during the preparation of the curable resin composition, it is preferably 50°C to 130°C.

[0055] The melting point of the epoxy resin shall be the value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin shall be the value measured by the method (ring-ball method) in accordance with JIS K 7234:1986.

[0056] The epoxy resin content in the curable resin composition is preferably 0.5% to 50% by mass, and more preferably 2% to 30% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc.

[0057] (Hardening agent) The curing agent included in the curable resin composition is not particularly limited as long as it contains a specific curing agent, and can be selected according to the desired properties of the curable resin composition. The specific curing agent may have only hydroxyl groups attached to aromatic rings to which electron-donating groups are attached, or it may have hydroxyl groups attached to aromatic rings to which electron-donating groups are attached, and hydroxyl groups attached to aromatic rings to which electron-donating groups are not attached.

[0058] From the viewpoint of curing properties at low temperatures, the proportion of the specific curing agent in the curing agent is preferably 20% by mass or more of the total curing agent, and more preferably 30% by mass or more. There is no particular upper limit on the proportion of the specific curing agent in the curing agent. From the viewpoint of balancing the properties of the cured product, the proportion of the specific curing agent in the curing agent may be 90% by mass or less of the total curing agent, or 80% by mass or less.

[0059] From the viewpoint of low-temperature rapid curing, the specific curing agent preferably has a structure obtained by novolacizing a phenol compound to which an electron-donating group is attached, and more preferably has a structure obtained by novolacizing a phenol compound to which an electron-donating group is attached in the ortho position. An example of a structure obtained by novolacizing a phenol compound to which an electron-donating group is attached in the ortho position is the structure represented by the following general formula (B).

[0060] [ka]

[0061] In general formula (B), R 1 Each of these independently represents an electron-donating base, and n is an integer from 0 to 10. In general formula (B), R 1 Each of these is preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and more preferably a methyl group (an orthocresol novolac structure).

[0062] Specific examples of curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. From the viewpoint of balancing curability and pot life, at least one selected from the group consisting of phenol curing agents, amine curing agents, and acid anhydride curing agents is preferred, and from the viewpoint of electrical reliability, phenol curing agents are more preferred.

[0063] Examples of phenol curing agents include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, these include polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; and the above phenolic compounds with dimethoxyp-xylene, bis(methoxymethyl)biphenyl, etc. Examples include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from the above phenolic compound; 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 compound and dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compound and 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 individually or in combination of two or more.

[0064] Among phenol curing agents, at least one selected from the group consisting of aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, triphenylmethane-type phenol resins, copolymerized phenol resins of benzaldehyde-type phenol resins and aralkyl-type phenol resins, and novolac-type phenol resins is preferred from the viewpoint of reflow resistance. From the viewpoint of low-temperature rapid curing, novolac-type phenol resins are more preferred.

[0065] Specific examples of aralkyl-type phenolic resins include phenolic resins represented by the following general formulas (XII) to (XIV).

[0066] [ka]

[0067] In equations (XII) to (XIV), R 23 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all 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 (preferably an electron-donating group in the case of a specific curing agent), and each of them 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 each of these may be the same or different. 'i' is an independent integer between 0 and 3, 'j' is an independent integer between 0 and 2, 'k' is an independent integer between 0 and 4, and 'p' is an independent integer between 0 and 4. 'n' is the average value, and each of these is an independent number between 0 and 10.

[0068] Among the phenolic resins represented by the above general formula (XII), i is 0 and R 23 MEH-7851 (Meiwa Chemicals Co., Ltd., product name), which consists entirely of hydrogen atoms, is available commercially.

[0069] A specific example of a dicyclopentadiene-type phenolic resin is the phenolic resin represented by the following general formula (XV).

[0070] [ka]

[0071] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms (preferably an electron-donating group in the case of a specific curing agent), and each of them may be the same or different. Each i independently represents an integer from 0 to 3. n is the average value and represents a number from 0 to 10.

[0072] A specific example of a triphenylmethane-type phenolic resin is the phenolic resin represented by the following general formula (XVI).

[0073] [ka]

[0074] In formula (XVI), R 30 and R 31 represents a monovalent organic group having 1 to 18 carbon atoms (preferably an electron-donating group in the case of a specific curing agent), and each of them may be the same or different. Each i is an independent integer from 0 to 3, and each k is an independent integer from 0 to 4. n is the average value and is a number from 0 to 10.

[0075] A specific example of a copolymerized phenolic resin of a benzaldehyde-type phenolic resin and an aralkyl-type phenolic resin is the phenolic resin represented by the following general formula (XVII).

[0076] [ka]

[0077] In formula (XVII), R 32 ~R 34This is a monovalent organic group with 1 to 18 carbon atoms (in the case of a specific curing agent, R 32 and R 34 ∫(preferably an electron-donating base), and each may be the same or different. Each i is an independent integer between 0 and 3, each k is an independent integer between 0 and 4, and each q is an independent integer between 0 and 5. l and m are the average values, each an independent number between 0 and 11, provided that the sum of l and m is a number between 1 and 11.

[0078] Specific examples of novolac-type phenolic resins include phenolic resins represented by the following general formula (XVIII).

[0079] [ka]

[0080] In formula (XVIII), R 35 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms (preferably a hydrogen atom), and each of them may be the same or different. 36 represents a monovalent organic group having 1 to 18 carbon atoms (preferably an electron-donating group in the case of a specific curing agent), and each of them may be the same or different. Each i independently represents an integer from 0 to 3. n is the average value and represents a number from 0 to 10.

[0081] In the above general formulas (XII) to (XVIII), R 22 ~R 36 The statement "they may all be identical or all different" refers, for example, to the i Rs in equation (XII). 22 This means that all of them may be identical or mutually different. 23 ~R 36 Regarding this as well, it means that the number of each element included in the formula may all be the same or they may be different from each other. Also, R 22 ~R 36 These can be the same or different. For example, R 22 and R 23 All of them may be the same or different, R30 and R 31 All of them may be the same or different.

[0082] 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 does not become too high, and the viscosity of the curable resin composition during melt molding tends to be low. The average n in one molecule is preferably set in the range of 0 to 4.

[0083] The functional group equivalent of the curing agent (hydroxyl group equivalent in the case of a phenol curing agent) is not particularly limited. From the viewpoint of balancing 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.

[0084] If the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handling during the manufacture of the sealing resin composition, it is more preferably 50°C to 130°C.

[0085] The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0086] The equivalent ratio of epoxy resin to curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in curing agent / number of functional groups in epoxy resin), is not particularly limited. From the viewpoint of minimizing unreacted components, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is even more preferable to set it in the range of 0.8 to 1.2.

[0087] (Curing accelerator) The curable resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited, and conventionally known ones can be used. For example, cycloamidine compounds such as 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo(4,3,0)nonene, 5,6-dibutylamino-1,8-diazabicyclo(5,4,0)undecene-7, tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-tri Examples include imidazole compounds such as azine and 2-heptadecylimidazole, organophosphine compounds such as trialkylphosphine (tributylphosphine, etc.), dialkylarylphosphine (dimethylphenylphosphine, etc.), alkyldiarylphosphine (methyldiphenylphosphine, etc.), triphenylphosphine, alkyl-substituted triphenylphosphine, and quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenolic resins, and other compounds having intramolecular polarization, as well as derivatives thereof. Furthermore, examples include phenylborone salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The hardening accelerator may be used individually or in combination of two or more types.

[0088] From the viewpoint of promoting the reaction between epoxy resin and curing agent at low temperatures, it is preferable that the curable resin composition contains an imidazole compound.

[0089] When a curable resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (total of epoxy resin and curing agent). When the amount of curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin component, it tends to result in a good molded product with a curing speed that is not too fast.

[0090] (Inorganic filler) The curable resin composition may contain an inorganic filler. In particular, when the curable resin composition is used as a encapsulant for semiconductor packages, it is preferable to include an inorganic filler.

[0091] The type of inorganic filler is not particularly limited. Specifically, examples include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fossterite, steatite, spinel, mullite, titania, talc, clay, mica, and other inorganic materials. Inorganic fillers with flame retardant properties may also be used. Examples of flame retardant inorganic fillers include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxides, and zinc borate. Among these, fused silica is preferred from the viewpoint of reducing the coefficient of thermal expansion, 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. Examples of inorganic filler states include powder, beads formed from spherical powder, and fibers.

[0092] When a curable resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, it is preferable that the inorganic filler content be 30% to 90% by volume of the total curable resin composition, more preferably 35% to 80% by volume, and even more preferably 40% to 70% by volume. When the inorganic filler content is 30% or more by volume of the total curable resin composition, the properties of the cured product, such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus, tend to improve. When the inorganic filler content is 90% or less by volume of the total curable resin composition, the increase in viscosity of the curable resin composition is suppressed, and the fluidity tends to improve, resulting in better moldability.

[0093] 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 curable resin composition 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.

[0094] The volume-average particle size of inorganic fillers in a curable resin composition or its cured product can be measured by known methods. For example, the inorganic filler can be extracted from the curable resin composition or cured product using an organic solvent, nitric acid, aqua regia, etc., 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 by a laser diffraction scattering particle size distribution analyzer. 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, polishing the resulting cross-section, and observing it with a scanning electron microscope. Furthermore, it can also be measured by continuously observing the two-dimensional cross-section of the cured product using a FIB (Focused Ion Beam Scanning Electron Microscope) and performing three-dimensional structural analysis.

[0095] From the viewpoint of the fluidity of the curable resin composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably widely distributed.

[0096] [Various additives] In addition to the components described above, the curable resin composition may also contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, and stress relievers, as exemplified below. The curable resin composition may also contain, as necessary, various additives well known in the art, in addition to those exemplified below.

[0097] (Coupling agent) If the curable resin composition contains an inorganic filler, a coupling agent may be included to improve the adhesion between the resin component and the inorganic filler. Examples of known coupling agents include silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, as well as titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0098] When the curable resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass, per 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, the adhesion to the frame tends to improve further. When the amount of the coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, the moldability of the package tends to improve further.

[0099] (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 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 an 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.

[0100] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0<X≦0.5, m is a positive number)

[0101] 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 parts by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass, based on 100 parts by mass of the resin component.

[0102] (Release agent) The curable resin composition may contain a release agent from the viewpoint of obtaining good mold release property with the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, examples include higher fatty acids such as carnauba wax, montanic acid, and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.

[0103] When a curable resin composition contains a release agent, the amount is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the resin component. When the amount of release agent is 0.01 parts by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When it is 15 parts by mass or less, better adhesion tends to be obtained.

[0104] (Flame retardant) The curable resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specifically, examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardant may be used alone or in combination of two or more types.

[0105] If the curable resin composition contains a flame retardant, the amount is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 300 parts by mass, and more preferably 2 to 150 parts by mass, per 100 parts by mass of the resin component.

[0106] (Coloring agent) The curable resin composition may further contain a colorant. Examples of known colorants include carbon black, organic dyes, organic pigments, titanium dioxide, red lead, and red iron oxide. The amount of colorant can be appropriately selected depending on the purpose. One colorant may be used alone, or two or more colorants may be used in combination.

[0107] (Stress reliever) The curable resin composition may contain stress-relieving agents such as silicone oil and silicone rubber particles. Including stress-relieving agents can further reduce package warping and cracking. Examples of commonly used stress-relieving agents (flexible agents) 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. One type of stress-relieving agent may be used alone, or two or more types may be used in combination. Among these, silicone-based stress-relieving agents are preferred. Examples of silicone-based stress-relieving agents include those having epoxy groups, those having amino groups, and those modified with polyether.

[0108] (Method for preparing a curable resin composition) The method for preparing the curable resin composition is not particularly limited. A common method involves thoroughly mixing predetermined amounts of components using a mixer or the like, then melt-kneading them using a mixing roll, extruder, or the like, followed by cooling and pulverization. More specifically, for example, a method involves uniformly stirring and mixing predetermined amounts of the above-mentioned components, then kneading them using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, followed by cooling and pulverization.

[0109] The curable resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25°C and atmospheric pressure). The shape of the curable resin composition when it is solid is not particularly limited, and examples include powder, granules, and tablets. When the curable resin composition is in tablet form, the dimensions and mass are preferably such that they conform to the molding conditions of the package, from the viewpoint of ease of handling.

[0110] <Electronic Components and Devices> An electronic component device according to one embodiment of the present disclosure comprises an element and a cured product of the above-mentioned curable resin composition for sealing the element. Examples of electronic component devices include those in which elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) are mounted on support members such as lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, and the resulting element section is sealed with a curable resin composition. More specifically, a DIP (Dual Inline) has a structure in which elements are fixed on a lead frame, the terminal parts of the elements such as bonding pads and the lead parts are connected by wire bonding, bumps, etc., and then sealed by transfer molding or the like using a curable resin composition. Examples include common resin-encapsulated ICs such as 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); TCP (Tape Carrier Package) having a structure in which elements connected to a tape carrier with bumps are encapsulated in a curable resin composition; COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc. having a structure in which elements connected to wiring formed on a support member by wire bonding, flip-chip bonding, solder, etc., are encapsulated in a curable resin composition; and BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package) having a structure in which elements are mounted on the surface of a support member with terminals for connecting to a wiring board formed on the back side, and after connecting the elements to the wiring formed on the support member by bumps or wire bonding, the elements are encapsulated in a curable resin composition. Furthermore, curable resin compositions can also be suitably used in printed circuit boards.

[0111] Methods for encapsulating electronic components using a curable resin composition include low-pressure transfer molding, injection molding, and compression molding. Among these, low-pressure transfer molding is the most common. Another method is called molded underfill (MUF). Molded underfill is a method that performs both the sealing of the gap between the semiconductor chip and the substrate (underfill) and the sealing of the top of the semiconductor chip (overmolding) in one step. [Examples]

[0112] The above embodiments will be described in detail below with reference to examples, but the scope of the above embodiments is not limited to these examples.

[0113] [Preparation of curable resin composition] A curable resin composition was prepared by mixing the following materials in the composition (parts by mass) shown in Table 1 and performing roll kneading under the conditions of a kneading temperature of 80°C and a kneading time of 15 minutes.

[0114] Epoxy resin 1: Triphenylmethane-type epoxy resin in which an epoxy-containing group is bonded to an aromatic ring to which an electron-donating group (methyl group) is bonded (Nippon Kayaku Co., Ltd., product name "EPPN-501HY"), epoxy equivalent 196 g / eq, melting point 106°C Epoxy resin 2: Biphenyl-type epoxy resin in which an epoxy-containing group is bonded to an aromatic ring to which an electron-donating group (methyl group) is bonded (Mitsubishi Chemical Corporation, product name "YX-4000H"), epoxy equivalent 196 g / eq, melting point 106°C Epoxy resin 3: An epoxy resin having a biphenyl structure (25% by mass) in which an electron-donating group is not bonded to the aromatic ring, and a triphenylmethane structure (75% by mass) in which an electron-donating group is not bonded to the aromatic ring (Mitsubishi Chemical Corporation, product name "YL6677"), epoxy equivalent 155-170 g / eq, softening point 60°C-100°C A mixture of epoxy resin 4:4,4'-biphenyldiylbis(glycidyl ether) and 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl (mass ratio 1:1) (Mitsubishi Chemical Corporation, product name "YL6121"), epoxy equivalent 170-180 g / eq, softening point 105°C

[0115] Curing agent 1: Triphenylmethane-type phenolic resin (Meiwa Chemical Industries, Ltd., product name "MEH7500-3S") in which electron-donating groups are not bonded to the aromatic ring to which epoxy-containing groups are bonded, hydroxyl group equivalent 103 g / eq, softening point 83°C Hardener 2: Orthocresol novolac resin (Meiwa Chemicals Co., Ltd., product name "MEH5100-5S"), hydroxyl group equivalent 116 g / eq, softening point 64°C Hardening agent 3: Phenol novolac resin without electron-donating groups bonded to the aromatic ring (Hitachi Chemical Co., Ltd., product name "HP-850N"), hydroxyl group equivalent 106 g / eq, softening point 83°C

[0116] Curing accelerator 1: Additive of tributylphosphine and benzoquinone Curing accelerator 2: 2-phenyl-4-methylimidazole Coupling agent 1: 3-methacryloxypropyltrimethoxysilane Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane Release agent 1: Montanoic acid ester Coloring agent 1: Carbon black

[0117] Stress relaxation agent 1: Styrene-indene copolymer resin Stress-relieving agent 2: Liquid silicone having epoxy and polyether groups in its side chains. Inorganic filler 1: Spherical fused silica (volume average particle size 5 μm) Inorganic filler 2: Fine spherical fused silica (volume average particle size 0.5 μm)

[0118] [Assessment of liquidity] A spiral flow test was performed as an indicator for evaluating fluidity. Specifically, using a spiral flow measurement mold conforming to EMMI-1-66, the flow distance (cm) of the curable resin composition was determined at a molding pressure of 6.9 MPa, with curing times of 120 seconds / 175°C and 600 seconds / 130°C. The results are shown in Table 1.

[0119] [Geltime evaluation] Measurements were performed on 3g of the curable resin composition using a Curlastometer from JSR Trading Co., Ltd. at temperatures of 175°C and 130°C, and the time until the torque curve rose was defined as the gel time (seconds). The results are shown in Table 1.

[0120] [Evaluation of curing properties at low temperatures] Using an APIC G-Line (MZ674-1) transfer molding machine, mold array packages (MAPs) were molded onto 240mm x 74mm square Cu plates with a curable resin composition to a molding thickness of 500μm at the temperatures and times shown in Table 1 (molding pressure 3MPa). The appearance of the strip surface and the CAL portion after molding was checked, and the curability at low temperatures was evaluated according to the following criteria. The results are shown in Table 1.

[0121] A: The surface of the molded product on the substrate has sufficient curing properties, and there are no blisters or other defects in the calcium carbonated areas. B: The surface of the molded product on the substrate has sufficient curability, but there are blisters and other defects in the calcium carbonated areas. C: Uncured areas will occur.

[0122] [Table 1]

[0123] As shown in Table 1, the curable resin compositions of the examples using epoxy resins having epoxy-containing groups bonded to aromatic rings that do not have electron-donating groups (part of epoxy resin 3 and epoxy resin 4) and a curing agent having hydroxyl groups bonded to aromatic rings that do have electron-donating groups (curing agent 2) exhibited better low-temperature curing properties compared to the curable resin compositions of the comparative examples that did not satisfy these conditions. Furthermore, the curable resin compositions of Examples 3 and 4, which used an imidazole compound as a curing accelerator, exhibited better curability at low temperatures compared to the curable resin compositions of Examples 1 and 2, which used a curing accelerator other than the imidazole compound.

Claims

1. A curable resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin comprises an epoxy-containing group bonded to an aromatic ring to which an electron-donating group is not bonded, and the curing agent comprises a curing agent having a hydroxyl group bonded to an aromatic ring to which an electron-donating group is bonded.

2. The curable resin composition according to claim 1, wherein the electron-donating group is at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, amino groups, and methoxy groups.

3. The curable resin composition according to claim 1 or claim 2, wherein the epoxy resin having an epoxy-containing group bonded to an aromatic ring to which the electron-donating group is not bonded has a biphenyl structure.

4. The curable resin composition according to any one of claims 1 to 3, wherein the curing agent having a hydroxyl group bonded to an aromatic ring to which the electron-donating group is bonded has a structure obtained by novolacizing the phenol compound to which the electron-donating group is bonded.

5. The curing agent having a hydroxyl group bonded to an aromatic ring to which the electron-donating group is bonded has a structure obtained by novolacizing a phenol compound to which the electron-donating group is bonded in the ortho position, according to any one of claims 1 to 4.

6. A curable resin composition according to any one of claims 1 to 5, further comprising an imidazole compound.

7. A curable resin composition according to any one of claims 1 to 6, for use as a encapsulant for electronic component devices.

8. An electronic component device comprising an element and a cured product of a curable resin composition according to any one of claims 1 to 7 for sealing the element.

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