Curable resin composition and electronic component device

Abstract

The present disclosure relates to a curable resin composition and an electronic component device. The curable resin composition comprises a curable resin and a compound represented by the following general formula (A). In the general formula (A), R 11 ~R 16 Each independently represents a hydrogen atom, ‑CH2OH or ‑CH2OR 17 , R 17 represents an alkyl group having 1 to 3 carbon atoms. 11 ~R 16 At least one of the following represents ‑CH2OR 17 . #imgabs0#

Description

Technical Field

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

[0002] With the miniaturization, lightness, and high performance of electronic devices in recent years, the density of installation has been continuously promoted. As a result, the mainstream of electronic component devices has changed from the existing pin insertion type packaging to surface mounting type packaging such as integrated circuit (IC) and large scale integration (LSI).

[0003] The installation method of the surface mount package is different from that of the existing pin insertion package. That is, when the pin is installed on the wiring board, the existing pin insertion package is to insert the pin into the wiring board and then solder it from the back of the wiring board, so the package is not directly exposed to high temperature. However, in the surface mount package, the entire electronic component device is processed using a solder bath, a reflow device, etc., so the package is directly exposed to the soldering temperature (reflow temperature). As a result, in the case of moisture absorption of the package, the moisture expands rapidly during soldering due to moisture absorption, and the generated vapor pressure acts as a peeling stress, thereby causing peeling between the inserts such as components and lead frames and the sealing material, which sometimes becomes the cause of package cracks, poor electrical characteristics, etc. Therefore, it is desired to develop a sealing material that has excellent adhesion to the insert and thus excellent solder heat resistance (reflow resistance).

[0004] In order to meet the above requirements, the use of silane coupling agents as a reforming material of the inorganic filler contained in the sealing material is studied. Specifically, the use of epoxy-containing silane coupling agents or amino-containing silane coupling agents (for example, see Patent Document 1), the use of sulfur-containing silane coupling agents (for example, see Patent Document 2), etc. are studied.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] Patent Document 1: Japanese Patent Laid-Open No. 11-147939

[0008] Patent Document 2: Japanese Patent Application Publication No. 2000-103940 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] However, in the method of using an epoxy-containing silane coupling agent or an amino-containing silane coupling agent, the effect of improving the adhesion of the lead frame surface to metal is sometimes insufficient. In addition, when using a sulfur-containing silane coupling agent, there is a problem that the effect of improving the adhesion to metals (precious metals such as gold and silver) and to substrates on which Ag plating is performed on copper lead frames is insufficient. Furthermore, additives containing sulfur atoms sometimes corrode copper wiring, and a method of improving adhesion without using additives containing sulfur atoms is required.

[0011] The present disclosure has been made in view of the above-mentioned circumstances, and an object of the present disclosure is to provide a curable resin composition having excellent adhesion to metal in a cured state, and an electronic component device including a device sealed with the curable resin composition.

[0012] [Technical means to solve the problem]

[0013] The specific method for achieving the above-mentioned subject is as follows.

[0014] <1> A curable resin composition comprising a curable resin and a compound represented by the following general formula (A).

[0015] [Chemistry 1]

[0016]

[0017] [In the general formula (A), R 11 ~R 16 Each independently represents a hydrogen atom, -CH2OH or -CH2OR 17 , R 17 represents an alkyl group with 1 to 3 carbon atoms; R 11 ~R 16 At least one of -CH2OR 17 ]

[0018] <2> The curable resin composition according to <1>, wherein the compound represented by the general formula (A) comprises R 11 ~R 16 At least four of them are -CH2OR 17 Represents the compound.

[0019] <3> The curable resin composition according to <1>, wherein the compound represented by the general formula (A) comprises R 11 ~R 16 All by -CH2OR 17 Represents the compound.

[0020] <4> The curable resin composition according to any one of <1> to <3>, further comprising an inorganic filler.

[0021] <5> The curable resin composition according to any one of <1> to <4>, wherein the curable resin includes an epoxy resin.

[0022] <6> The curable resin composition according to <5>, wherein the epoxy resin comprises at least one selected from the group consisting of biphenyl epoxy resin, distilbene epoxy resin, diphenylmethane epoxy resin, sulfur atom-containing epoxy resin, novolac epoxy resin, dicyclopentadiene epoxy resin, triphenylmethane epoxy resin, copolymer epoxy resin and aralkyl epoxy resin.

[0023] <7> The curable resin composition according to any one of <1> to <6>, further comprising a curing agent.

[0024] <8> The curable resin composition according to <7>, wherein the curing agent comprises at least one selected from the group consisting of aralkyl phenol resins, dicyclopentadiene phenol resins, triphenylmethane phenol resins, copolymerized phenol resins of triphenylmethane phenol resins and aralkyl phenol resins, and novolac phenol resins.

[0025] <9> The curable resin composition according to any one of <1> to <8>, further comprising a curing accelerator.

[0026] <10> The curable resin composition according to <9>, wherein the curing accelerator contains a phosphonium compound.

[0027] <11> The curable resin composition according to <10>, wherein the phosphonium compound includes a compound represented by the following general formula (I-1).

[0028] [Chemistry 2]

[0029]

[0030] [In the general formula (I-1), R 1 ~R 3 Each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 At least two of them can be bonded to each other to form a ring structure, R 4 ~R 7 Each independently represents a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and R 4 ~R 7 At least two of them may be bonded to each other to form a ring structure]

[0031] <12> The curable resin composition according to <11>, wherein the compound represented by the general formula (I-1) includes a compound represented by the following general formula (I-2).

[0032] [Chemistry 3]

[0033]

[0034] [In the general formula (I-2), R 1 ~R 3 Each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 At least two of them can be bonded to each other to form a ring structure, R 4 ~R 6 Each independently represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 4 ~R 6 At least two of them may be bonded to each other to form a ring structure]

[0035] <13> An electronic component device including a device and a cured product of the curable resin composition according to any one of <1> to <12> that seals the device.

[0036] [Effects of the Invention]

[0037] According to the present disclosure, there are provided a curable resin composition having excellent adhesion to metal in a cured state, and an electronic component device including a device sealed with the curable resin composition. DETAILED DESCRIPTION

[0038] Hereinafter, the form for implementing the present disclosure is described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, its constituent elements (including element steps, etc.) are not necessarily required except for the cases specifically indicated. The same is true for numerical values ​​and their ranges, and the present disclosure is not limited.

[0039] In the present disclosure, the term "process" includes processes that are independent of other processes and processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved.

[0040] In the present disclosure, in a numerical range represented by “to”, numerical values ​​described before and after including “to” are respectively regarded as the minimum value and the maximum value.

[0041] In the numerical range recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range may also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in the present disclosure, the upper limit or lower limit of the numerical range may also be replaced by the value shown in the embodiment.

[0042] In the present disclosure, each component may include a plurality of substances corresponding thereto. When a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the plurality of substances present in the composition.

[0043] In the present disclosure, particles corresponding to each component may include multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to the value for the mixture of the multiple types of particles present in the composition unless otherwise specified.

[0044] <Curing resin composition>

[0045] The curable resin composition of the present disclosure contains a curable resin and a compound represented by the following general formula (A) (hereinafter, sometimes referred to as specific alkylated melamine).

[0046] [Chemistry 4]

[0047]

[0048] In the general formula (A), R 11 ~R 16 Each independently represents a hydrogen atom, -CH2OH or -CH2OR 17 , R 17 represents an alkyl group having 1 to 3 carbon atoms. 11 ~R 16 At least one of -CH2OR 17 .

[0049] According to the research conducted by the present inventors, it is known that a curable resin composition containing a specific alkylated melamine has excellent adhesion to metals (precious metals such as gold and silver) and to substrates with Ag plated on a copper lead frame in a cured state. Although the reason is not clear, it is presumed that the specific alkylated melamine in the cured product forms a coordination bond with the metal.

[0050] The curable resin composition containing the specific alkylated melamine has excellent adhesion to metal in the cured state, so when used as a sealing material for a package including a lead frame whose surface is made of metal at least, peeling between the lead frame and the sealing material can be suppressed. Therefore, the reflow resistance is excellent.

[0051] The curable resin composition of the present disclosure contains a curable resin and a specific alkylated melamine, and may contain other components such as an inorganic filler, a curing agent, and a curing accelerator as necessary.

[0052] Hereinafter, each component contained in the curable resin composition of the present disclosure will be described in detail.

[0053] (Specific alkylated melamine)

[0054] The curable resin composition of the present disclosure contains a specific alkylated melamine. The specific alkylated melamine may be used alone or in combination of two or more types having different structures.

[0055] As R in the general formula (A) 17 , examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0056] The specific alkylated melamine is preferably R 11 ~R 16 At least three of them are -CH2OR 17 The compound represented by 11 ~R 16 At least four of them are -CH2OR 17 The compound represented by R 11 ~R 16 All by -CH2OR 17 The compound represented by R 11 ~R 16 All compounds are represented by -CH2OCH3.

[0057] As a specific example of the specific alkylated melamine, the compound represented by the following formula is mentioned.

[0058] [Chemistry 5]

[0059]

[0060] The proportion of the compound represented by formula (A1) in the specific alkylated melamine is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

[0061] The content of the specific alkylated melamine in the curable resin composition is not particularly limited. From the viewpoint of sufficiently obtaining the effect of improving the adhesion to precious metals such as gold and silver and the adhesion to substrates on which Ag plating is performed on copper lead frames, for example, relative to 100 parts by mass of the total of the curable resin contained in the curable resin composition and the curing agent used as needed (hereinafter also referred to as "resin component"), it is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 2.5 parts by mass or more. From the viewpoint of curability, for example, relative to 100 parts by mass of the resin component, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

[0062] (hardening resin)

[0063] The curable resin is not particularly limited as long as it forms a three-dimensional crosslinked structure by reaction, and may be thermosetting or photocurable. From the viewpoint of mass production, thermosetting is preferred. The curable resin may be a curable resin that is cured by self-polymerization, or a curable resin that is cured by reaction with a curing agent, a crosslinking agent, or the like.

[0064] The functional group that can undergo a curing reaction contained in the curable resin is not particularly limited, and examples thereof include: epoxy groups, cyclic ether groups such as oxetane groups, hydroxyl groups, carboxyl groups, amino groups, acryloyl groups, methacryloyl groups, isocyanate groups, maleimide groups, alkenyl groups, etc. From the perspective of balancing the characteristics of the sealing material, a curable resin containing a cyclic ether group is preferred, and a curable resin containing an epoxy group (epoxy resin) is more preferred.

[0065] When the curable resin is 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.

[0066] Specifically, there can be mentioned: a resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolac resin, and then epoxidizing the novolac resin, i.e., a novolac type epoxy resin (phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, etc.); a resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst to obtain a triphenylmethane type phenol resin, and then epoxidizing the triphenylmethane type phenol resin The resin obtained is triphenylmethane type epoxy resin; the resin obtained by co-condensing the phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst to obtain a novolac resin and epoxidizing the novolac resin is a copolymerized epoxy resin; diphenylmethane type epoxy resin as diglycidyl ether of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resin as diglycidyl ether of alkyl-substituted or unsubstituted biphenol; stilbene type epoxy resin as diglycidyl ether of stilbene series phenol compound; sulfur-containing epoxy resin as diglycidyl ether of bisphenol S, etc.; epoxy resin as glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; epoxy resin as diglycidyl ether of phthalic acid, isophthalic acid, Glycidyl ester epoxy resins of glycidyl esters of polycarboxylic acid compounds such as phthalic acid and tetrahydrophthalic acid; glycidylamine epoxy resins obtained by replacing the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with glycidyl groups; dicyclopentadiene epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; alicyclic epoxy resins such as diepoxy vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane obtained by epoxidizing an olefin bond in the molecule; and p-xylene-modified phenol resins. p-xylene modified epoxy resin as glycidyl ether; m-xylene modified epoxy resin as glycidyl ether of m-xylene modified phenol resin; terpene modified epoxy resin as glycidyl ether of terpene modified phenol resin; dicyclopentadiene modified epoxy resin as glycidyl ether of dicyclopentadiene modified phenol resin; cyclopentadiene modified epoxy resin as glycidyl ether of cyclopentadiene modified phenol resin; polycyclic aromatic ring modified epoxy resin as glycidyl ether of polycyclic aromatic ring modified phenol resin; naphthalene type epoxy resin as glycidyl ether of phenol resin containing naphthalene ring; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bonds using peracids such as peracetic acid;Aralkyl epoxy resins are resins obtained by epoxidizing aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins. In addition, epoxy resins such as epoxides of silicone resins and epoxides of acrylic resins can also be used as epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0067] Among the epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, at least one epoxy resin selected from the group consisting of biphenyl epoxy resins, stilbene epoxy resins, diphenylmethane epoxy resins, sulfur-containing epoxy resins, novolac epoxy resins, dicyclopentadiene epoxy resins, triphenylmethane epoxy resins, copolymerized epoxy resins, and aralkyl epoxy resins is preferred (these are referred to as "specific epoxy resins"). The specific epoxy resins may be used alone or in combination of two or more.

[0068] When the epoxy resin contains a specific epoxy resin, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, based on the entire epoxy resin, from the viewpoint of exerting the performance of the specific epoxy resin.

[0069] From the viewpoint of fluidity, the specific epoxy resin is preferably a biphenyl type epoxy resin, a distyrene type epoxy resin, a diphenylmethane type epoxy resin or a sulfur atom-containing epoxy resin, and from the viewpoint of heat resistance, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin or an aralkyl type epoxy resin. Specific examples of preferred epoxy resins are shown below.

[0070] 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. In the epoxy resin represented by the following general formula (II), R 8 The positions of the oxygen atoms in the molecule are 4-position and 4'-position, and the 3, 3', 5, and 5'-positions are methyl groups, and the other R 8 YX-4000H (trade name of Mitsubishi Chemical Co., Ltd.) with hydrogen atoms, all R 8 4,4'-bis(2,3-epoxypropoxy)biphenyl with hydrogen atoms, all R 8 For hydrogen atoms and R 8 The positions of the oxygen atoms in the molecule are 4-position and 4'-position, and the 3, 3', 5, and 5'-positions are methyl groups, and the other R 8 In the case of a hydrogen atom, a mixed product such as YL-6121H (trade name of Mitsubishi Chemical Corporation) is available as a commercial product.

[0071] [Chemistry 6]

[0072]

[0073] 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, and all of them may be the same or different. n is an average value and represents a number of 0 to 10.

[0074] 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 The positions of the oxygen atoms in the molecule are 4-position and 4'-position, and the 3, 3', 5, and 5'-positions are methyl groups, and the other R 9 is a hydrogen atom, R 10 When all atoms are hydrogen atoms and R 9 Among the 3, 3', 5, and 5' positions, three are methyl groups, one is tert-butyl, and the other R 9 is a hydrogen atom, R 10 A mixed product in which all atoms are hydrogen atoms, etc.

[0075] [Chemistry 7]

[0076]

[0077] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. n is an average value and represents a number of 0 to 10.

[0078] The diphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferred. In the epoxy resin represented by the following general formula (IV), R 11 All hydrogen atoms, R 12 The positions of the oxygen atoms in the molecule are 4-position and 4'-position, and the 3, 3', 5, and 5'-positions are methyl groups, and the other R 12 YSLV-80XY (trade name of Nippon Steel Chemical & Material Co., Ltd.) or the like which is a hydrogen atom is available as a commercial product.

[0079] [Chemistry 8]

[0080]

[0081] In formula (IV), R 11 and R 12represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. n is an average value and represents a number of 0 to 10.

[0082] 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) can be cited. In the epoxy resin represented by the following general formula (V), R 13 The positions of the oxygen atoms in the molecule are 4-position and 4'-position, and the 3 and 3'-positions are tert-butyl, the 6 and 6'-positions are methyl, and the other R 13 YSLV-120TE (trade name of Nippon Steel Chemical & Material Co., Ltd.) or the like which is a hydrogen atom is available as a commercial product.

[0083] [Chemistry 9]

[0084]

[0085] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. n is an average value and represents a number of 0 to 10.

[0086] 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, it is preferably 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 glycidyl etherification method, and more preferably an epoxy resin represented by the following general formula (VI). In the epoxy resin represented by the following general formula (VI), R 14 All hydrogen atoms, R 15 ESCN-190, ESCN-195 (trade name of Sumitomo Chemical Co., Ltd.) etc. where R is methyl and i=1; 14 All of them are hydrogen atoms, i = 0 N-770, N-775 (DIC Co., Ltd., trade name) etc.; 14 All hydrogen atoms, i = 0 and i = 1, R 15 A styrene-modified phenol novolac type epoxy resin having a -CH(CH3)-Ph moiety, namely, YDAN-1000-10C (trade name of Nippon Steel Chemical & Material Co., Ltd.); a styrene-modified phenol novolac type epoxy resin having a -CH(CH3)-Ph moiety; ... 14 All are hydrogen atoms, i = 1, R 15 The part with methyl group and i=2, R 15A benzyl-modified cresol novolac-type epoxy resin in which one of the moieties is a methyl group and the other is a benzyl group is commercially available.

[0087] [Chemistry 10]

[0088]

[0089] In formula (VI), R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 15 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0090] The dicyclopentadiene-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferred. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) with i=0 is available as a commercial product.

[0091] [Chemistry 11]

[0092]

[0093] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0094] The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material. For example, it is preferably an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenol resin obtained from an aromatic aldehyde compound and a phenolic compound, and more preferably an epoxy resin represented by the following general formula (VIII). Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Co., Ltd., trade name), EPPN-502H (Nippon Kayaku Co., Ltd., trade name), etc., in which i is 0 and k is 0, can be obtained as commercial products.

[0095] [Chemistry 12]

[0096]

[0097] In formula (VIII), R 17 and R 18The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i each independently represents an integer of 0 to 3, and k each independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10.

[0098] 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 using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, it is preferably an epoxy resin obtained by glycidyl etherifying a novolac-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton, and more preferably an epoxy resin represented by the following general formula (IX). In the epoxy resin represented by the following general formula (IX), R 21 NC-7300 (trade name, Nippon Kayaku Co., Ltd.) or the like, which is a methyl group, i is 1, j is 0, and k is 0, is commercially available.

[0099] [Chemistry 13]

[0100]

[0101] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different. i represents an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4. l and m are average values, which are numbers from 0 to 10, and (l+m) represents a number from 0 to 10. The end of the epoxy resin represented by formula (IX) is any 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 the same as those of R in formula (IX) 19 ~R 21 , i, j and k are the same as those defined above. n is 1 (when bonded via a methylene group) or 0 (when bonded not via a methylene group).

[0102] [Chemistry 14]

[0103]

[0104] Examples of the epoxy resin represented by the general formula (IX) include random copolymers randomly containing one structural unit and m structural units, alternating copolymers alternately containing one structural unit and m structural units, copolymers regularly containing one structural unit and m structural units, block copolymers containing one structural unit and m structural units in a block form, etc. Any of these may be used alone, or two or more thereof may be used in combination.

[0105] As the copolymerized epoxy resin, a methoxynaphthalene-cresol formaldehyde co-condensation type epoxy resin containing the following two structural units in a random, alternating or block order, i.e., EPICLON HP-5000 (DIC Corporation, trade name) represented by the following general formula is also preferred. In the following general formula, n and m are respectively average values, and are numbers from 0 to 10, and (n+m) represents a number from 0 to 10, and preferably n and m are respectively average values, and are numbers from 1 to 9, and (n+m) represents a number from 2 to 10.

[0106] [Chemistry 15]

[0107]

[0108] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin prepared from a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof as a raw material. For example, it is preferably an epoxy resin obtained by glycidyl etherifying a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof, and more preferably an epoxy resin represented by the following general formula (X) and general formula (XI).

[0109] In the epoxy resin represented by the following general formula (X), i is 0 and R 38 NC-3000S (trade name of Nippon Kayaku Co., Ltd.) with a hydrogen atom was used to convert i to 0 and R 38 The epoxy resin having hydrogen atoms and all R 8 CER-3000 (trade name of Nippon Kayaku Co., Ltd.) which is a mixture of epoxy resins containing hydrogen atoms can be obtained as commercial products. In addition, ESN-175 (trade name of Nippon Steel Chemical & Material Co., Ltd.) in which l is 0, j is 0, and k is 0 among the epoxy resins represented by the following general formula (XI) can be obtained as commercial products.

[0110] [Chemistry 16]

[0111]

[0112] In formula (X) and formula (XI), R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 37, R 39 ~R 41 The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and l is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0113] Regarding R in the general formula (II) to (XI) 8 ~R 21 and R 37 ~R 41 , the term "may be all the same or different" means, for example, that 8 to 88 R in formula (II) 8 All may be the same or different. 9 ~R 21 and R 37 ~R 41 , means that the numbers of each contained in the formula may be the same or different. 8 ~R 21 and R 37 ~R 41 They may be the same or different. For example, R 9 With R 10 All can be the same or different.

[0114] In addition, the monovalent organic group having 1 to 18 carbon atoms in the general formulae (III) to (XI) is preferably an alkyl group or an aryl group.

[0115] In the general formulae (II) to (XI), n is an average value, and is preferably independently in the range of 0 to 10. If n is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the curable resin composition during melt molding will decrease, and there is a tendency to suppress the occurrence of poor filling, deformation of the bonding wire (metal wire connecting the element and the lead), etc. n is more preferably set in the range of 0 to 4.

[0116] The functional group equivalent of the curable resin (epoxy equivalent in the case of epoxy resin) is not particularly limited. From the perspective of balancing various properties such as formability, 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.

[0117] The softening point or melting point of the curable resin is not particularly limited, but is preferably 40° C. to 180° C. from the viewpoint of moldability and reflow resistance, and is more preferably 50° C. to 130° C. from the viewpoint of workability during preparation of the curable resin composition.

[0118] In the present disclosure, the softening point refers to a value measured by the ring and ball method of Japanese Industrial Standard (JIS) K 7234:1986.

[0119] In the present disclosure, the melting point refers to a value measured by a visual method in accordance with JIS K 0064:1992.

[0120] 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, more preferably 2% by mass to 30% by mass.

[0121] (Hardener)

[0122] The curable resin composition may contain a curing agent. The type of the curing agent is not particularly limited, and can be selected according to the type of the curable resin, the desired properties of the curable resin composition, and the like.

[0123] When the curable resin is an epoxy resin, examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. From the viewpoint of both curability and pot life, at least one selected from the group consisting of phenol curing agents, amine curing agents, and acid anhydride curing agents is preferred, and from the viewpoint of electrical reliability, phenol curing agents are more preferred.

[0124] Examples of the phenol curing agent include phenol resins and polyphenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyphenol 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, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; and polyphenol resins synthesized from the phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, and the like. Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; p-xylene and / or m-xylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; dicyclopentadiene-type phenol resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above-mentioned phenolic compounds and dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these, etc. Furthermore, as phenol curing agents, monohydric phenol compounds having one phenolic hydroxyl group in one molecule can also be listed. These phenol curing agents can be used alone or in combination of two or more.

[0125] Among the phenol curing agents, from the viewpoint of reflow resistance, at least one selected from the group consisting of aralkyl phenol resins, dicyclopentadiene phenol resins, triphenylmethane phenol resins, copolymerized phenol resins of triphenylmethane phenol resins and aralkyl phenol resins, and novolac phenol resins is preferred (these are referred to as "specific phenol curing agents"). The specific phenol curing agents may be used alone or in combination of two or more.

[0126] When the curing agent includes a specific phenol curing agent, the content of the specific phenol curing agent is preferably 30% by mass or more, more preferably 50% by mass or more, based on the entire curing agent from the viewpoint of fully exerting these performances.

[0127] As the aralkyl phenol resin, phenol aralkyl resins and naphthol aralkyl resins synthesized from phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. can be cited. The aralkyl phenol resin can also be copolymerized with other phenol resins. As the copolymerized aralkyl phenol resins, the copolymerized phenol resins of triphenylmethane phenol resin and aralkyl phenol resin, the copolymerized phenol resins of salicylaldehyde phenol resin and aralkyl phenol resin, the copolymerized phenol resins of novolac phenol resin and aralkyl phenol resin, etc. can be cited.

[0128] The aralkyl phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of phenol compounds and naphthol compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof. For example, the phenol resins represented by the following general formulas (XII) to (XIV) are preferred.

[0129] [Chemistry 17]

[0130]

[0131] In formula (XII) to formula (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 22 , R 24 , R 25 and R 28 represents a monovalent organic group having 1 to 18 carbon atoms, and all 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 all of them may be the same or different. i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and p is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0132] In the phenol resin represented by the general formula (XII), i is 0 and R 23 MEH-7851 (trade name, Meiwa Chemical Co., Ltd.), etc., which are all hydrogen atoms, are commercially available.

[0133] Among the phenol resins represented by the general formula (XIII), XL-225, XLC (trade name of Mitsui Chemicals, Inc.), MEH-7800 (trade name of Meiwa Chemicals, Inc.), and the like, in which i is 0 and k is 0, are commercially available.

[0134] In the phenol resin represented by the general formula (XIV), SN-170 (trade name of Nippon Steel Chemical & Material Co., Ltd.) in which j is 0, k is 0 and p is 0, and SN-170 (trade name of Nippon Steel Chemical & Material Co., Ltd.) in which j is 0, k is 0 and p is 0, and SN-170 in which j is 0, k is 1 and R is 0. 27 SN-395 (trade name of Nippon Steel Chemical & Material Co., Ltd.) in which p is 0 and a hydroxyl group is available as a commercial product.

[0135] The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferred. Among the phenol resins represented by the following general formula (XV), a phenol resin in which i is 0 can be obtained as a commercial product.

[0136] [Chemistry 18]

[0137]

[0138] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0139] The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained using an aromatic aldehyde compound and a phenolic compound as raw materials, and is preferably a phenol resin represented by the following general formula (XVI).

[0140] Among the phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, Meiwa Chemicals Co., Ltd.) in which i is 0 and k is 0 is commercially available.

[0141] [Chemistry 19]

[0142]

[0143] In formula (XVI), R 30 and R 31 The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i is an integer of 0 to 3, and k is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0144] The copolymerized phenol resin of triphenylmethane type phenol resin and aralkyl type phenol resin is not particularly limited as long as it is a copolymerized phenol resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenol resin. For example, a phenol resin represented by the following general formula (XVII) is preferred.

[0145] [Chemistry 20]

[0146]

[0147] In formula (XVII), R 32 ~R 34The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i is an integer of 0 to 3, k is an integer of 0 to 4, and q is an integer of 0 to 5. l and m are average values ​​and are numbers of 0 to 11. The total of l and m is a number of 1 to 11.

[0148] The novolac-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. For example, a phenol resin represented by the following general formula (XVIII) is preferred.

[0149] In the phenol resin represented by the following general formula (XVIII), i is 0, R 35 Tamanol 758, 759 (trade names of Arakawa Chemical Industries, Ltd.) and H-4 (trade name of Meiwa Chemicals Co., Ltd.) which are all hydrogen atoms are commercially available.

[0150] [Chemistry 21]

[0151]

[0152] In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 36 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0153] In the general formula (XII) to (XVIII), R 22 ~R 36 The phrase "may be all the same or different" means, for example, that i R in formula (XII) 22 All of them may be the same or different from each other. 23 ~R 36 , means that the numbers of each contained in the formula may be all the same or different from each other. 22 ~R 36 They may be the same or different. 22 and R 23 Can be all the same or different, R 30 and R 31 They may all be the same or different.

[0154] The n in the general formula (XII) to the general formula (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the curable resin composition during melt molding will also be low, which makes it difficult to cause filling defects and deformation of bonding wires (metal wires connecting elements and leads). The average n in one molecule is preferably set in the range of 0 to 4.

[0155] Examples of the monophenol compound include "Tinuvin 405", "Tinuvin 900", "Tinuvin 99-2", "Tinuvin 326", "Tinuvin 384-2" and "Tinuvin 928" (all from BASF).

[0156] The functional group equivalent of the hardener (hydroxyl equivalent in the case of a phenol hardener) is not particularly limited, but is preferably 70 g / eq to 1000 g / eq, more preferably 80 g / eq to 600 g / eq, from the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability.

[0157] The softening point or melting point of the curing agent is not particularly limited, but is preferably 40° C. to 180° C. from the viewpoint of moldability and reflow resistance, and more preferably 50° C. to 130° C. from the viewpoint of workability during production of the curable resin composition.

[0158] The equivalent ratio of the curable resin to the curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (number of functional groups in the curing agent / number of functional groups in the curable resin) is not particularly limited. From the perspective of suppressing the respective unreacted components to a small extent, 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 perspective of formability and reflow resistance, it is further preferably set in the range of 0.8 to 1.2.

[0159] (hardening accelerator)

[0160] The curable resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and can be selected according to the type of the curable resin, the desired properties of the curable resin composition, and the like.

[0161] From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include: tertiary phosphines such as triphenylphosphine, diphenyl(p-toluene)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl-alkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine; and quinone compounds having intramolecular polarization formed by the addition of compounds having π bonds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 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; and compounds having π bonds such as diazonophenylmethane. Compounds; reacting the tertiary phosphine with 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 Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl and then undergoing a dehydrohalogenation process; salts of tetrasubstituted phosphoniums such as tetraphenylphosphonium and tetrasubstituted borates such as tetra-p-toluene borate; salts of tetrasubstituted phosphoniums and anions deprotonated from phenol compounds, salts of tetrasubstituted phosphoniums and anions deprotonated from carboxylic acid compounds, etc.

[0162] The phosphonium compound preferably includes a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific hardening accelerator).

[0163] [Chemistry 22]

[0164]

[0165] In formula (I-1), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 Two or more of them can bond to each other to form a ring structure, R 4 ~R 7 are 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 them can be bonded to each other to form a ring structure.

[0166] As R of the general formula (I-1) 1~R 3 The "hydrocarbon group having 1 to 18 carbon atoms" mentioned herein includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0167] 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 still more preferably 4 to 6 carbon atoms, from the viewpoint of fluidity.

[0168] The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or may be an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of easy production, a linear or branched aliphatic hydrocarbon group is preferred.

[0169] As a straight-chain or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, allyl, and vinyl groups can be listed. A straight-chain or branched aliphatic hydrocarbon group may or may not have a substituent. As a substituent, alkoxy groups such as methoxy, ethoxy, n-butoxy, and tert-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl, amino, and halogen atoms can be listed. A straight-chain or branched aliphatic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When a straight-chain 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 preferred, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferred, and an n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, and n-octyl group are further preferred.

[0170] As the alicyclic hydrocarbon group having 3 to 18 carbon atoms, specifically, cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, cycloalkenyl groups such as cyclopentenyl and cyclohexenyl, etc. can be cited. The alicyclic hydrocarbon group may or may not have a substituent. As the substituent, alkyl groups such as methyl, ethyl, n-butyl, and tert-butyl, alkoxy groups such as methoxy, ethoxy, n-butoxy, and tert-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, halogen atoms, etc. can be cited. The alicyclic hydrocarbon group may have two or more substituents, and the substituents in this case 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, it is preferably an unsubstituted cycloalkyl group, more preferably an unsubstituted cycloalkyl group having 4 to 10 carbon atoms, and further preferably a cyclohexyl group, a cyclopentyl group, and a cycloheptyl group.

[0171] The aromatic hydrocarbon group having a carbon number of 6 to 18 preferably has a carbon number of 6 to 14, and more preferably 6 to 10. The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, n-butyl, and tert-butyl, alkoxy groups such as methoxy, ethoxy, n-butoxy, and tert-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, halogen atoms, and the like. The aromatic hydrocarbon group may have two or more substituents, and the substituents may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6 to 18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

[0172] As the aromatic hydrocarbon group having 6 to 18 carbon atoms, specifically, phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, n-butoxyphenyl, tert-butoxyphenyl, etc. can be cited. The position of the substituent in these aromatic hydrocarbon groups can be any of the ortho position, meta position and para position. From the viewpoint of fluidity, it is preferably an unsubstituted aryl group having 6 to 12 carbon atoms or a carbon number of 6 to 12 including a substituent, more preferably an unsubstituted aryl group having 6 to 10 carbon atoms or a carbon number of 6 to 10 including a substituent, and further preferably a phenyl group, p-tolyl and p-methoxyphenyl.

[0173] As R of the general formula (I-1) 1 ~R 3 The term "R 1 ~R 3 Two or more of them can bond to each other to form a ring structure" means R 1 ~R 3 In the case of two or three bonds in the , the whole becomes a divalent or trivalent hydrocarbon group. 1 ~R 3 Examples of the substituents include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethynylene, propynylene, and butynylene, aralkylene groups such as methylenephenylene, arylene groups such as phenylene, naphthylene, and anthracene, and substituent groups such as alkylene ...

[0174] As R in the general formula (I-1) 4 ~R 7 The "organic group having 1 to 18 carbon atoms" mentioned herein includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and which may be substituted or unsubstituted, an aromatic hydrocarbon group, an aliphatic hydrocarbonoxy group, an aromatic hydrocarbonoxy group, an acyl group, a hydrocarbonoxycarbonyl group, and an acyloxy group.

[0175] Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group include: 1 ~R 3 Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group represented are described above.

[0176] Examples of the aliphatic hydrocarbon oxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, cyclopropyloxy, cyclohexyloxy, cyclopentyloxy, allyloxy, vinyloxy and other oxy groups having a structure in which an oxygen atom is bonded to the aliphatic hydrocarbon group; and groups in which these aliphatic hydrocarbon oxy groups are further substituted by an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom or the like.

[0177] Examples of the aromatic hydrocarbon oxy group include oxy groups having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group, such as phenoxy, methylphenoxy, ethylphenoxy, methoxyphenoxy, butoxyphenoxy, and phenoxyphenoxy; and groups in which these aromatic hydrocarbon oxy groups are further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

[0178] Examples of the acyl group include aliphatic hydrocarbon carbonyl groups such as formyl, acetyl, ethylcarbonyl, butyryl, cyclohexylcarbonyl, and allylcarbonyl, and aromatic hydrocarbon carbonyl groups such as phenylcarbonyl and methylphenylcarbonyl; and groups in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted by an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.

[0179] Examples of the hydrocarbon oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, allyloxycarbonyl, and cyclohexyloxycarbonyl, aromatic hydrocarbon oxycarbonyl groups such as phenoxycarbonyl and methylphenoxycarbonyl, and groups in which these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy 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.

[0180] Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy, and cyclohexylcarbonyloxy groups, aromatic hydrocarbon carbonyloxy groups such as phenylcarbonyloxy and methylphenylcarbonyloxy groups, and groups in which these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.

[0181] As R of the general formula (I-1) 4 ~R 7 The term "R 4 ~R 7 "Two or more of the R 4 ~R 7bond, and as a whole, a divalent to tetravalent organic group can be formed. 4 ~R 7 , exemplified are: alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethynylene, propynylene, and butynylene, aralkylene groups such as methylenephenylene, arylene groups such as phenylene, naphthylene, and anthracene, and the like, substituents that can form a ring structure, oxy groups or dioxy groups thereof, etc. These substituents may be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, and the like.

[0182] As R of the general formula (I-1) 4 ~R 7 , and is not particularly limited. For example, it is preferably independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. Among them, from the viewpoint of the ease of obtaining the raw materials, it is preferably a hydrogen atom, a hydroxyl group, an unsubstituted or substituted aryl group selected from the group consisting of an alkyl group and an alkoxy group, or a chain or cyclic alkyl group. As the unsubstituted or substituted aryl group selected from the group consisting of an alkyl group and an alkoxy group, there are exemplified: phenyl, p-tolyl, m-tolyl, o-tolyl, p-methoxyphenyl, etc. As the chain or cyclic alkyl group, there are exemplified: methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, octyl, cyclohexyl, etc. From the viewpoint of curability, R 4 ~R 7 When all are hydrogen atoms, or R 4 ~R 7 At least one of them is a hydroxyl group and the rest are all hydrogen atoms.

[0183] In the general formula (I-1), R 1 ~R 3 Two or more of them are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and R 4 ~R 7 All are hydrogen atoms or at least one is a hydroxyl group and the rest are all hydrogen atoms. 1 ~R 3 All of the groups in the group are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and R 4 ~R 7 All are hydrogen atoms or at least one is a hydroxyl group and the rest are all hydrogen atoms.

[0184] From the viewpoint of rapid curing properties, the specific curing accelerator preferably contains a compound represented by the following general formula (I-2).

[0185] [Chemistry 23]

[0186]

[0187] In formula (I-2), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 Two or more of them can bond to each other to form a ring structure, R 4 ~R 6 are independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, R 4 ~R 6 Two or more of them can be bonded to each other to form a ring structure.

[0188] R in the general formula (I-2) 1 ~R 6 The specific examples are respectively the same as R in the general formula (I-1) 1 ~R 6 The specific examples and preferred ranges are the same.

[0189] 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.

[0190] The specific hardening accelerator is available, for example, as an adduct of a tertiary phosphine compound and a quinone compound.

[0191] Specific examples of the tertiary phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, tri(4-ethylphenyl)phosphine, tri(4-n-propylphenyl)phosphine, tri(4-n-butylphenyl)phosphine, tri(isopropylphenyl)phosphine, tri(tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, and tri(4-ethoxyphenyl)phosphine. From the viewpoint of formability, triphenylphosphine and tributylphosphine are preferred.

[0192] Specific examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.

[0193] The curable resin composition may contain a curing accelerator other than the phosphonium compound.

[0194] Specific examples of the curing accelerator other than the phosphonium compound include: diazabicycloolefins such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 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 addition of maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-diphenylimidazolone, and the like to these compounds. Compounds with intramolecular polarization formed by quinone compounds such as methyl benzoquinone, 2,6-dimethyl benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds with π bonds such as diazonium methane; cyclic amidinium compounds such as tetraphenyl borate of DBU, tetraphenyl borate of DBN, tetraphenyl borate of 2-ethyl-4-methylimidazole, and tetraphenyl borate of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide, etc.

[0195] When the curable resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more of the entire curing accelerator.

[0196] When the curable resin composition contains a curing accelerator, the amount of the curing accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the resin component. If the amount of the curing accelerator is 0.1 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to cure well in a short time. If the amount of the curing accelerator is 30 parts by mass or less relative to 100 parts by mass of the resin component, there is a tendency to obtain a good molded product whose curing speed is not too fast.

[0197] (Inorganic filler)

[0198] 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 to contain an inorganic filler.

[0199] The type of inorganic filler is not particularly limited. Specifically, it can be listed as inorganic materials such as spherical silica, crystalline silica, glass, aluminum oxide, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica. Inorganic fillers with flame retardant effects can also be used. As inorganic fillers with flame retardant effects, composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, magnesium and zinc composite hydroxides, zinc borate, etc. can be listed. Among them, from the viewpoint of reducing the linear expansion coefficient, spherical silica is preferred, and from the viewpoint of high thermal conductivity, aluminum oxide is preferred. The inorganic filler can be used alone or in combination of two or more. As the state of the inorganic filler, it can be listed as powder, particles sphericalizing the powder, fibers, etc.

[0200] In the case where the curable resin composition includes an inorganic filler, its content is not particularly limited. From the perspective of fluidity and strength, it is preferably 30% to 90% by volume of the curable resin composition as a whole, more preferably 35% to 80% by volume, and further preferably 40% to 70% by volume. If the content of the inorganic filler is more than 30% by volume of the curable resin composition as a whole, there is a tendency that the thermal expansion coefficient, thermal conductivity, elastic modulus and other properties of the cured product are further improved. If the content of the inorganic filler is less than 90% by volume of the curable resin composition as a whole, there is a tendency that the viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the formability becomes better.

[0201] 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 50 μm, and more preferably 0.5 μm to 30 μm.

[0202] If the volume average particle size is 0.2 μm or more, the viscosity of the curable resin composition tends to be further suppressed. If the volume average particle size is 50 μm or less, the filling property of 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) by a laser diffraction scattering particle size distribution measuring device.

[0203] The volume average particle size of the inorganic filler in the curable resin composition or its cured product can be measured using a known method. For example, an inorganic filler is extracted from a curable resin composition or a cured product using an organic solvent, nitric acid, aqua regia, etc., and a dispersion is prepared by fully dispersing it using an ultrasonic disperser or the like. The dispersion can be used to measure the volume average particle size of the inorganic filler based on the volume-based particle size distribution measured using a laser diffraction scattering particle size distribution measuring device. Alternatively, the cured product can be embedded in a transparent epoxy resin, etc., and a cross-section is obtained by grinding, and the volume average particle size of the inorganic filler is measured based on the volume-based particle size distribution obtained by observing the cross-section obtained using a scanning electron microscope. Furthermore, it can also be measured in the following manner: a two-dimensional cross-section observation of the cured product is continuously performed using a FIB device (focused ion beam SEM), etc., and a three-dimensional structural analysis is performed.

[0204] 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 distributed in a wide range.

[0205] [Various additives]

[0206] In addition to the above components, the curable resin composition may also contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, and stress relaxants as exemplified below. In addition to the additives exemplified below, the curable resin composition may also contain various additives such as ultraviolet absorbers known in the art as needed.

[0207] (Coupling agent)

[0208] When the curable resin composition contains an inorganic filler, a coupling agent may be contained in order to improve the adhesion between the resin component and the inorganic filler. Examples of the coupling agent include silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureide silane, and vinylsilane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0209] When the curable resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass, relative to 100 parts by mass of the inorganic filler. If the amount of the coupling agent is 0.05 parts by mass or more relative to 100 parts by mass of the inorganic filler, there is a tendency for the adhesion with the frame to be further improved. If the amount of the coupling agent is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, there is a tendency for the moldability of the package to be further improved.

[0210] (Ion Exchanger)

[0211] The curable resin composition may also contain an ion exchanger. In particular, when the curable resin composition is used as a sealing molding material, it is preferred to contain an ion exchanger from the viewpoint of improving the moisture resistance and high temperature storage characteristics of the electronic component device including the sealed element. There is no particular limitation on the ion exchanger, and existing known ion exchangers can be used. Specifically, hydrotalcite compounds, and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth, etc. can be listed. The ion exchanger can be used alone or in combination of two or more. Among them, the hydrotalcite represented by the following general formula (B) is preferred.

[0212] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O······(B)

[0213] (0<X≦0.5, m is a positive number)

[0214] When the curable resin composition contains an ion exchanger, the content of the ion exchanger is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions, for example, preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the resin component.

[0215] (Release Agent)

[0216] From the viewpoint of obtaining good demolding properties from the mold during molding, the curable resin composition may also contain a release agent. The release agent is not particularly limited, and a known release agent can be used. Specifically, examples include: carnauba wax, higher fatty acids such as octadecanoic acid and stearic acid, higher fatty acid metal salts, ester waxes such as octadecanoic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. The release agent may be used alone or in combination of two or more.

[0217] When the curable resin composition contains a release agent, the amount of the release agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the resin component. If the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency that sufficient releasability can be obtained. If it is 15 parts by mass or less, there is a tendency that better adhesion can be obtained.

[0218] (Flame Retardant)

[0219] The curable resin composition may also contain a flame retardant. The flame retardant is not particularly limited, and a conventionally known flame retardant may be used. Specifically, examples include organic compounds 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.

[0220] When the curable resin composition contains a flame retardant, the amount of the flame retardant is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect, for example, preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass, relative to 100 parts by mass of the resin component.

[0221] (Colorant)

[0222] The curable resin composition may further contain a colorant. Examples of the colorant include carbon black, organic dyes, organic pigments, titanium oxide, red lead, iron oxide and other known colorants. The content of the colorant may be appropriately selected according to the purpose, etc. The colorant may be used alone or in combination of two or more.

[0223] (Stress Relaxant)

[0224] The curable resin composition may also include stress relaxants such as silicone oil and silicone rubber particles. By including a stress relaxant, the warping deformation of the package and the occurrence of package cracks can be further reduced. As a stress relaxant, commonly used known stress relaxants (flexible agents) can be cited. Specifically, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene, natural rubber (natural rubber, NR), acrylonitrile butadiene rubber (acrylonitrile butadiene rubber, NBR), acrylic rubber, urethane rubber, silicone powder and other rubber particles, methyl methacrylate-styrene-butadiene copolymer (Methacrylate methylstyrene butadiene, MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, copolymers of indenes such as indene, alkyl indene, and styrene, alkyl styrene and phenols and aromatic olefins such as coumarone as other constituent monomers, etc. The stress relaxants may be used alone or in combination of two or more.

[0225] (Method for preparing curable resin composition)

[0226] The method for preparing the curable resin composition is not particularly limited. As a general method, the following method can be cited: after the components of the prescribed amount are fully mixed by a mixer, etc., melt-kneading is performed by a grinding roll, an extruder, etc., and then cooled and crushed. More specifically, for example, the following method can be cited: the prescribed amount of the components is uniformly stirred and mixed, and kneaded and cooled by a kneader, a roll, an extruder, etc. preheated to 70°C to 140°C, and then crushed.

[0227] The curable resin composition is preferably solid at room temperature and pressure (e.g., 25° C., atmospheric pressure). The shape of the curable resin composition when solid is not particularly limited, and examples thereof include powder, granules, sheets, pellets, granules, etc. From the viewpoint of operability, the size and mass of the curable resin composition when it is in sheet or granule form are preferably the size and mass that meet the molding conditions of the package.

[0228] <Electronic components and devices>

[0229] An electronic component device according to one embodiment of the present disclosure includes: a device; and a cured product of the curable resin composition that seals the device.

[0230] Examples of electronic component devices include electronic component devices in which a component portion (active components such as semiconductor chips, transistors, diodes, and thyristors, passive components such as capacitors, resistors, and coils) is mounted on a supporting member such as a lead frame, a wired conveyor tape, a wiring board, glass, a silicon wafer, or an organic substrate and sealed with a curable resin composition.

[0231] More specifically, there can be cited general resin-sealed ICs such as dual inline package (DIP), plastic leaded chip carrier (PLCC), quad flat package (QFP), small outline package (SOP), small outline J-lead package (SOJ), thin small outline package (TSOP), and thin quad flat package (TQFP), which have a structure in which a component is fixed on a lead frame and a terminal portion and a lead portion of the component such as a bonding pad are connected by wire bonding, bumps, etc., and then sealed by transfer molding using a curable resin composition; tape carrier package (TCP), which has a structure in which a component connected to a carrier tape by bumps is sealed using a curable resin composition; chip on substrate (Chip On Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which have a structure in which a curable resin composition is used to seal components connected to wiring formed on a supporting member by wire bonding, flip chip bonding, solder, etc.; ball grid array (BGA), chip size package (CSP), multi-chip package (MCP), etc., which have a structure in which components are mounted on the surface of a supporting member with a wiring board connection terminal formed on the back, and the components are connected to the wiring formed on the supporting member by bumps or wire bonding, and then the components are sealed with a curable resin composition. In addition, the curable resin composition can also be preferably used in printed wiring boards.

[0232] Examples of a method for sealing an electronic component device using a curable resin composition include low-pressure transfer molding, injection molding, and compression molding. Among these, the low-pressure transfer molding method is common.

[0233] [Example]

[0234] Hereinafter, the present disclosure will be specifically described by way of examples, but the scope of the present disclosure is not limited to these examples.

[0235] [Preparation of curable resin composition]

[0236] The following materials were mixed in the composition (parts by mass) shown in Table 1, and roll kneaded at a kneading temperature of 80° C. and a kneading time of 15 minutes to prepare curable resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3.

[0237] (Epoxy resin)

[0238] Epoxy resin 1: methoxynaphthalene-cresol formaldehyde co-condensation type epoxy resin with epoxy equivalent of 250 g / eq and softening point of 58°C (DIC Corporation, trade name "HP-5000")

[0239] Epoxy resin 2: biphenyl type epoxy resin with epoxy equivalent of 196 g / eq and softening point of 106°C (Mitsubishi Chemical Corporation, trade name "YX-4000H")

[0240] (Hardener)

[0241] Hardener 1: phenol aralkyl resin with a hydroxyl equivalent of 175 g / eq and a softening point of 70°C (Meiwa Chemicals Co., Ltd., trade name "MEH-7800SS")

[0242] Hardener 2: melamine-modified phenolic resin with a hydroxyl equivalent of 120 g / eq and a softening point of 90°C

[0243] Hardener 3: 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (BASF, trade name "Tinuvin 405")

[0244] · Hardening accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone

[0245] · Coupling agent 1: 3-glycidyloxypropyltrimethoxysilane

[0246] · Coupling agent 2: 3-phenylaminopropyltrimethoxysilane

[0247] Release agent 1: montan wax (Clariant, trade name "Licowax E")

[0248] Release agent 2: polyethylene oxide (Dainichi Chemical Industry Co., Ltd., trade name "PE-A")

[0249] Colorant: Carbon black (Mitsubishi Chemical Co., Ltd., product name "MA600")

[0250] Ion exchanger: hydrotalcite

[0251] Stress relaxants: indene oligomers

[0252] Flame retardant: triphenylphosphine oxide

[0253] Alkylated melamine: a compound represented by formula (A1) (Sanwa Chemical Co., Ltd., trade name "MW-390")

[0254] Methylated urea resin: a compound represented by the following formula (Sanwa Chemical Co., Ltd., trade name "MX-270")

[0255] [Chemistry 24]

[0256]

[0257] Inorganic filler: Silica filler (volume average particle size 19μm)

[0258] [Evaluation of Curable Resin Composition]

[0259] The properties of the curable resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were evaluated by the following property tests. The evaluation results are shown in Table 1 below. The curable resin composition was molded by a transfer molding machine at a mold temperature of 175° C., a molding pressure of 8.3 MPa, and a curing time of 120 seconds. Subsequently, post-curing was performed at 175° C. for 5 hours to obtain a molded product.

[0260] (Evaluation of Adhesion Strength 1)

[0261] The method is used to form a bonding surface with an area of ​​about 10 mm on the surface of a substrate (PPF) with a size of 9 mm × 9 mm and a Ni-Pd-Au plated copper lead frame or a substrate (Ag) with an Ag plated copper lead frame. 2 A round shaped object.

[0262] Using an adhesive strength tester manufactured by DAGE, force was applied to the molded object in the shear direction at a height of 50 μm from the substrate surface at 25°C (room temperature) at a measuring speed of 50 μm / second to measure the force when the substrate and the molded object broke or peeled off.

[0263] (Evaluation of Adhesion Strength 2)

[0264] Evaluation of adhesive strength 2 was performed in the same manner as in evaluation of adhesive strength 1, except that the measurement was performed in a state where the substrate was heated to 260°C.

[0265] [Table 1]

[0266]

[0267]

[0268] As is clear from the evaluation results in Table 1, the curable resin compositions of Examples 1 and 2 containing specific alkylated melamine are superior in adhesive strength at 260° C. to the curable resin compositions of Comparative Example 1 not containing specific alkylated melamine and Comparative Examples 2 and 3 containing methylated urea resin instead of specific alkylated melamine.

[0269] The entire contents of the disclosure of Japanese Patent Application No. 2020-170631 filed on October 8, 2020 are incorporated into this specification by reference.

[0270] All documents, patent applications, and technical specifications described in this specification are cited and incorporated into this specification to the same extent as if each document, patent application, and technical specification was specifically and individually described as being incorporated by reference.

Claims

1. A curable resin composition comprising a curable resin, a curing agent, an inorganic filler, and a compound represented by the following general formula (A), The hardening resin comprises epoxy resin, The hardener comprises a phenol hardener, The content of the inorganic filler is 30 volume % to 90 volume % of the entire curable resin composition; In the general formula (A), R 11 ~R 16 Each independently represents a hydrogen atom, -CH2OH or -CH2OR 17 , R 17 represents an alkyl group with 1 to 3 carbon atoms; R 11 ~R 16 At least one of -CH2OR 17 .

2. The curable resin composition according to claim 1, wherein the compound represented by the general formula (A) comprises R 11 ~R 16 At least four of them are -CH2OR 17 Represents the compound.

3. The curable resin composition according to claim 1, wherein the compound represented by the general formula (A) comprises R 11 ~R 16 All by -CH2OR 17 Represents the compound.

4. The curable resin composition according to any one of claims 1 to 3, wherein the epoxy resin comprises at least one selected from the group consisting of biphenyl epoxy resins, stilbene epoxy resins, diphenylmethane epoxy resins represented by the following general formula (IV), sulfur-containing epoxy resins, novolac epoxy resins represented by the following general formula (VI), dicyclopentadiene epoxy resins, triphenylmethane epoxy resins represented by the following general formula (VIII), copolymerized epoxy resins represented by the following general formula (IX) and the following general formula (IX-3), and aralkyl epoxy resins represented by the following general formula (X) and the following general formula (XI); In formula (IV), R 11 and R 12 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; n is an average value and represents a number from 0 to 10; In formula (VI), R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different; R 15 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i represents an integer of 0 to 3 independently; n is an average value and represents a number of 0 to 10; In formula (VIII), R 17 and R 18 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i represents an integer of 0 to 3, k represents an integer of 0 to 4, and n is an average value and represents a number of 0 to 10; In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i represents an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4; l and m are average values, which are numbers of 0 to 10, and (l+m) represents a number of 0 to 10; the end of the epoxy resin represented by formula (IX) is any 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 the same as those of R in formula (IX) 19 ~R 21 , i, j and k are the same as defined above; when the bond is through a methylene group, n is 1; when the bond is not through a methylene group, n is 0; in, The epoxy resin represented by the general formula (IX) is a random copolymer randomly comprising 1 structural unit and m structural units, an alternating copolymer alternately comprising 1 structural unit and m structural units, or a block copolymer comprising 1 structural unit and m structural units in a block form; In formula (IX-3), n and m are average values, respectively, and are numbers from 0 to 10, and (n+m) represents a number from 0 to 10; The epoxy resin represented by the general formula (IX-3) is a methoxynaphthalene-cresol formaldehyde co-condensation type epoxy resin containing the above two structural units in a random, alternating or block order; In formula (X) and formula (XI), R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different; R 37 , R 39 ~R 41 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, l is each independently an integer of 0 to 4; n is an average value and is each independently a number of 0 to 10.

5. The curable resin composition according to any one of claims 1 to 3, wherein the phenol curing agent comprises at least one selected from the group consisting of aralkyl phenol resins represented by the following general formulas (XII) to (XIV), dicyclopentadiene phenol resins, triphenylmethane phenol resins represented by the following general formula (XVI), copolymerized phenol resins of triphenylmethane phenol resins and aralkyl phenol resins represented by the following general formula (XVII), and novolac phenol resins represented by the following general formula (XVIII); In formula (XII) to formula (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different; R 22 , R 24 , R 25 and R 28 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; R 26 and R 27 represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and p is an integer of 0 to 4; n is an average value and is a number of 0 to 10; In formula (XVI), R 30 and R 31 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i is an integer of 0 to 3, k is an integer of 0 to 4, and n is an average value, which is a number of 0 to 10; In formula (XVII), R 32 ~R 34 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i is an integer of 0 to 3, k is an integer of 0 to 4, q is an integer of 0 to 5; l and m are average values ​​and are independently a number of 0 to 11; wherein, The sum of l and m is a number from 1 to 11; In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different; R 36 represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different; i represents an integer of 0 to 3 independently; and n represents an average value and a number of 0 to 10. 6 . The curable resin composition according to claim 1 , further comprising a curing accelerator. 7 . The curable resin composition according to claim 6 , wherein the curing accelerator comprises a phosphonium compound.

8. The curable resin composition according to claim 7, wherein the phosphonium compound comprises a compound represented by the following general formula (I-1); In the general formula (I-1), R 1 ~R 3 Each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 At least two of them can be bonded to each other to form a ring structure, R 4 ~R 7 Each independently represents a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and R 4 ~R 7 At least two of the alkyl groups may be bonded to each other to form a ring structure.

9. The curable resin composition according to claim 8, wherein the compound represented by the general formula (I-1) includes a compound represented by the following general formula (I-2); In the general formula (I-2), R 1 ~R 3 Each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 At least two of them can be bonded to each other to form a ring structure, R 4 ~R 6 Each independently represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 4 ~R 6 At least two of the alkyl groups may be bonded to each other to form a ring structure. 10 . An electronic component device comprising a device and a cured product of the curable resin composition according to claim 1 which seals the device.

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