Thermosetting resin composition, sealing material, and electronic component device

Abstract

The present invention provides: a thermosetting resin composition including a nitrogen atom-containing compound which is capable of improving tracking resistance; a sealing material; and an electronic component device. The thermosetting resin composition includes a thermosetting resin and a nitrogen atom-containing compound having a nitrogen atom content ratio, as calculated using equation (1), of 67 mass% or greater. (Equation 1) Nitrogen atom content ratio = (the number of nitrogen atoms in the compound × 14) × 100 / (molecular weight)

Description

Thermosetting resin compositions, encapsulants, and electronic component devices

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

[0002] In recent years, the demand for more advanced, lighter, and smaller electronic devices has led to increased density integration and even higher density mounting of electronic components. As a result, semiconductor packages used in these electronic devices are becoming smaller and smaller than ever before. Furthermore, the radio frequencies used for communication in electronic devices are also increasing.

[0003] For example, Patent Document 1 discloses a encapsulating resin material used in semiconductor packaging that includes one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole. According to Patent Document 1, using these specific triazole compounds results in excellent adhesion to metal components and superior reliability.

[0004] Japanese Patent Publication No. 2022-008598

[0005] Incidentally, in order to miniaturize semiconductor packages and to handle high frequencies, there is a demand for encapsulating materials for semiconductor devices that have excellent tracking resistance. However, Patent Document 1 does not mention the tracking resistance when using an encapsulating resin composition containing a specific triazole compound. In view of the above circumstances, this disclosure aims to provide a thermosetting resin composition, encapsulating material, and electronic component device containing a nitrogen atom-containing compound that can improve tracking resistance.

[0006] Having achieved the above-mentioned objectives, this disclosure includes the following: <1> A thermosetting resin composition comprising a thermosetting resin and a nitrogen atom-containing compound having a nitrogen atom content ratio of 67% by mass or more, calculated by the following formula (1): Nitrogen atom content ratio = (Number of nitrogen atoms in the compound × 14) × 100 / (Molecular weight) ... (1) <2> The thermosetting resin composition according to <1>, wherein the nitrogen atom-containing compound is a nitrogen-containing heterocyclic compound. <3> The thermosetting resin composition according to <1> or <2>, wherein the nitrogen atom-containing compound is a compound having a triazole structure. <4> The thermosetting resin composition according to any one of <1> to <3>, wherein the nitrogen atom-containing compound is 3,5-diamino-1,2,4-triazole. <5> The thermosetting resin composition according to any one of <1> to <4>, wherein the nitrogen atom content ratio of the nitrogen atom-containing compound is 70% by mass or more. <6> A thermosetting resin composition according to any one of <1> to <5>, wherein the thermosetting resin comprises an epoxy resin. <7> A thermosetting resin composition according to any one of <1> to <6>, further comprising at least one selected from the group consisting of a curing agent, a curing accelerator, and an inorganic filler. <8> A sealing material comprising the thermosetting resin composition according to any one of <1> to <7>. <9> An electronic component device comprising an element and a cured product of the sealing material according to <8> that seals the element.

[0007] According to this disclosure, it is possible to provide a thermosetting resin composition capable of forming an encapsulant with excellent tracking resistance, an encapsulant with excellent tracking resistance, and an electronic component device.

[0008] The embodiments are described in detail below. However, this disclosure is not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit this disclosure.

[0009] 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 the process is achieved. In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In 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. Also, in a described numerical range, the upper or lower limit of that range may be replaced with the value shown in the example. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, each component may contain multiple types of particles. If multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0010] <Thermosetting Resin Composition> A thermosetting resin composition according to one embodiment of the present disclosure comprises a thermosetting resin and a nitrogen atom-containing compound having a nitrogen atom content ratio of 67% by mass or more, calculated by the following formula (1): Nitrogen atom content ratio = (Number of nitrogen atoms in the compound × 14) × 100 / (Molecular weight) ... (1)

[0011] The encapsulant using the thermosetting resin composition of this disclosure exhibits excellent tracking resistance due to the inclusion of the nitrogen atom-containing compound. In particular, the tracking resistance of the encapsulant using the thermosetting resin composition of this disclosure can be evaluated according to the method described in the examples. Although the reason why the thermosetting resin composition exhibits excellent tracking resistance due to the inclusion of the nitrogen atom-containing compound is not clear, it is presumed that when a small current flows through the cured molded product, the char (carbon clumps) formed by the carbonization of the surface of the molded product is reduced, thereby suppressing the occurrence of tracking. Furthermore, the encapsulant using the thermosetting resin composition of this disclosure may also possess excellent characteristics such as a low molding shrinkage rate.

[0012] (Nitrogen Atom-Containing Compounds) The nitrogen atom-containing compounds included in the thermosetting resin composition of this disclosure are not particularly limited as long as the nitrogen atom content ratio described above is 67% by mass or more, and only need to contain at least one nitrogen atom in the molecule. Examples of such nitrogen atom-containing compounds include nitrogen-containing heterocyclic compounds, amino compounds, azo compounds, diazo compounds, amide compounds, imide compounds, imine compounds, nitrile compounds, nitro compounds, nitroso compounds, nitrate esters, nitrite esters, oxime compounds, and the like. Among these, nitrogen-containing heterocyclic compounds are preferred as the nitrogen atom-containing compound. This is because using nitrogen-containing heterocyclic compounds can further reduce char formation and obtain better tracking resistance.

[0013] Examples of nitrogen atom-containing compounds included in the thermosetting resin composition of this disclosure include nitrogen-containing heterocyclic compounds containing heterocyclic rings such as heterocyclic three-membered rings, heterocyclic four-membered rings, heterocyclic five-membered rings, and heterocyclic six-membered rings having at least one nitrogen atom. Specific examples of heterocyclic rings include nitrogen-containing heterocyclic three-membered rings such as aziridine structures, azirine structures, diaziridine structures, and diazirine structures. Also, examples of nitrogen-containing heterocyclic four-membered rings such as azetidine structures, azeto structures, diazetidine structures, and diazeto structures can be cited. Furthermore, examples of nitrogen-containing heterofive-membered rings include pyrrolidine, pyrrole, imidazolidine, pyrazolidine, imidazole, pyrazole, oxazolidine, isoxazolidine, oxazole, isoxazole, thiazolidine, isotizolidine, thiazol, isothiazole, triazole, fusazan, oxadiazole, thiadiazole, dioxazole, tetrazol, oxatetrazol, thiatetrazol, and pentazol structures. Moreover, examples of nitrogen-containing heterofive-membered rings include piperidine, pyrimidine, pyridazine, pyridine, piperazine, pyrazine, diazine, morpholine, oxazine, thiomorpholine, thiadin, hexahydro-1,3,5-triazine, triazine, tetrazine, and pentazine structures. Furthermore, examples include nitrogen-containing heteroseven-membered rings such as azepane, azepine, diazepane, diazepine, and thiazepine structures. Furthermore, examples include nitrogen-containing heteroseven-membered rings such as azocane and azosin structures. Moreover, nitrogen-containing heterocyclic compounds may also be compounds having fused rings. Specifically, examples include indole, isoindole, benzimidazole, benzotriazole, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, and acridine structures.

[0014] Among the nitrogen-containing heterocyclic compounds usable in the thermosetting resin compositions of this disclosure, those having a triazole structure are particularly preferred, and among these, the use of 3,5-diamino-1,2,4-triazole is more preferred. The nitrogen-containing heterocyclic compounds usable in the thermosetting resin compositions of this disclosure are not limited to 3,5-diamino-1,2,4-triazole, but include, for example, 3-amino-1,2,4-triazole (nitrogen atom content ratio of 67% by mass), 4-amino-1,2,4-triazole (nitrogen atom content ratio of 67% by mass), and the like.

[0015] Furthermore, it is preferable to use a nitrogen atom-containing compound with a nitrogen atom content of 70% by mass or more as the thermosetting resin composition usable in the present disclosure. For example, the nitrogen atom content of 3,5-diamino-1,2,4-triazole is 71% by mass.

[0016] Compounds such as 3,5-diamino-1,2,4-triazole may or may not have substituents. The substituents that compounds such as 3,5-diamino-1,2,4-triazole may have are not particularly limited, as long as the nitrogen atom content is 67% by mass or more, and include alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, alkoxy groups, mercapto groups, cycloalkyl groups, substituted cycloalkyl groups, heterocyclic groups, substituted heterocyclic groups, aryl groups, substituted aryl groups, heteroaryl groups, substituted heteroaryl groups, aryloxy groups, substituted aryloxy groups, halogen atoms, haloalkyl groups, cyano groups, nitro groups, nitroso groups, amino groups, amide groups, -C(O)H, -C(O)-, -S-, -S(O) ２ -, -OC(O)-O-, -C(O)-NR ｃ , -NR ｃ C(O)-N(R) ｃ ) ２ , -OC(O)-N(R ｃ ) ２ , acyl group, oxyacyl group, carboxyl group, carbamate group, sulfonyl group, sulfonamide group, sulfuryl group, etc. Here, R ｃ represents a hydrogen atom or an alkyl group.

[0017] Furthermore, the nitrogen atom-containing compound usable in the thermosetting resin composition of this disclosure preferably has a nitrogen atom content of 67% by mass or more, and an oxygen atom content of 30% by mass or less, more preferably an oxygen atom content of 20% by mass or less, even more preferably an oxygen atom content of 10% by mass or less, and even more preferably an oxygen atom content of 0% by mass. By setting the oxygen atom content within this range, char generation can be more effectively reduced and superior tracking resistance can be achieved. The oxygen atom content can be calculated using the formula [(number of oxygen atoms in the compound × 16) × 100 / (molecular weight)].

[0018] Furthermore, the nitrogen atom-containing compound usable in the thermosetting resin composition of this disclosure has a nitrogen atom content of 67% by mass or more, and preferably a carbon atom content of 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. By setting the carbon atom content within this range, char formation can be effectively reduced and excellent tracking resistance can be achieved. Furthermore, by setting the carbon atom content within this range, the polarity of the molecule increases, and phase separation from other organic compounds contained in the thermosetting resin composition can be achieved, thereby reducing the molding shrinkage rate. The carbon atom content can be calculated using the formula [(number of carbon atoms in the compound × 12) × 100 / (molecular weight)].

[0019] The amount of nitrogen atom-containing compound in the thermosetting resin composition as defined above is not particularly limited. From the viewpoint of obtaining a sufficient effect of improving tracking resistance, for example, it is preferable that the amount is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, even more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, per 100 parts by mass of the total of the thermosetting resin and the curing agent used as needed in the thermosetting resin composition (hereinafter also referred to as "resin component").

[0020] (Thermosetting resin) The thermosetting resin is not particularly limited as long as it forms a three-dimensional crosslinked structure by a reaction caused by heating. The thermosetting resin may cure by self-polymerization or by reaction with a curing agent, crosslinking agent, etc.

[0021] The functional groups that cause the reaction in the thermosetting resin are not particularly limited, and examples include epoxy groups, cyclic ether groups such as oxetanyl groups, hydroxyl groups, carboxyl groups, amino groups, acryloyl groups, isocyanate groups, maleimide groups, alkenyl groups, and the like. When using the thermosetting resin composition of this disclosure as a encapsulant, from the viewpoint of balancing the properties of the encapsulant, a thermosetting resin containing cyclic ether groups is preferred, and a thermosetting resin containing epoxy groups (epoxy resin) is more preferred.

[0022] If the thermosetting resin is an epoxy resin, the type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) are obtained by condensing or co-condensing a novolac resin obtained by condensing or co-condensing a novolac resin obtained by phenol compounds selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene under an acidic catalyst with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde under an acidic catalyst. Copolymer epoxy resins that have been modified; 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 substituted with a glycidyl group; dicyclopentadiene-type epoxy resins that are epoxidized from a co-condensation 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 dicyclopentadiene-modified phenol resins. 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.

[0023] When the thermosetting resin composition of the present disclosure is used as a sealing material, among the above epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, a copolymer type epoxy resin, and an aralkyl type epoxy resin are preferred. These are referred to as "specific epoxy resins"). The specific epoxy resin may be used alone or in combination of two or more.

[0024] When the epoxy resin contains a specific epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin, its content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total epoxy resin.

[0025] Among the specific epoxy resins, from the viewpoint of fluidity, a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, or a sulfur atom-containing type epoxy resin is more preferred, and from the viewpoint of heat resistance, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, or an aralkyl type epoxy resin is preferred. Hereinafter, specific examples of preferred epoxy resins are shown.

[0026] The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred. Among the epoxy resins represented by the following general formula (II), when the positions where oxygen atoms are substituted in R ８ are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups, and the other R ８ is a hydrogen atom, YX-4000H (Mitsubishi Chemical Corporation, trade name), all R ８ is a hydrogen atom, 4,4'-bis(2,3-epoxypropoxy)biphenyl, when all R ８ is a hydrogen atom and R ８ when the positions where oxygen atoms are substituted in R are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups, and the other R ８When the atom is a hydrogen atom, a mixed product such as YL-6121H (Mitsubishi Chemical Corporation, product name) is available commercially.

[0027]

[0028] 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 these may all be the same or all different. 'n' is an average value, representing a number between 0 and 10.

[0029] The stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, epoxy resins represented by the following general formula (III) are preferred. Among the epoxy resins represented by the following general formula (III), R ９ 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 ９ is a hydrogen atom, R １０ When all of them are hydrogen atoms, ９ Of the 3, 3', 5, and 5' positions, three are methyl groups, one is a t-butyl group, and the other R ９ is a hydrogen atom, R １０ A mixed product in which all atoms are hydrogen atoms, such as ESLV-210 (Sumitomo Chemical Co., Ltd., product name), is available commercially.

[0030]

[0031] In formula (III), R ９ and R １０ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. n is an average value and represents a number between 0 and 10.

[0032] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, epoxy resins represented by the following general formula (IV) are preferred. Among the epoxy resins represented by the following general formula (IV), R １１ All of them are hydrogen atoms, R １２Of 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 Chemical & Material Co., Ltd., product name), which contains hydrogen atoms, are available commercially.

[0033]

[0034] In formula (IV), R １１ and R １２ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. n is an average value and represents a number between 0 and 10.

[0035] Sulfur atom-containing epoxy resins are not particularly limited as long as they contain sulfur atoms. For example, epoxy resins represented by the following general formula (V) are included. 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 and 3' positions are t-butyl groups, the 6 and 6' positions are methyl groups, and the other R １３ Products such as YSLV-120TE (Nippon Steel Chemical & Material Co., Ltd., product name), which contains hydrogen atoms, are available commercially.

[0036]

[0037] In formula (V), R １３ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. n is an average value and represents a number between 0 and 10.

[0038] 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, epoxy resins obtained by epoxidizing novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and naphthol novolac resin using methods such as glycidyl etherification are preferred, and epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), R １４ All of them are hydrogen atoms, R １５The methyl group is i=1 in ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd., product name), R １４ All of them are hydrogen atoms, and 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 ga-CH(CH ３ YDAN-1000-10C (Nippon Steel Chemical & Material Co., Ltd., product name), R is a styrene-modified phenol novolac type epoxy resin having a )-Ph portion. １４ All of them are hydrogen atoms, i=1, R １５ The part where i is a methyl group and R １５ HP-5600 (DIC Corporation, trade name), a benzyl group-modified cresol novolac type epoxy resin having a moiety in which one of the moieties is a methyl group and the other is a benzyl group, is available commercially.

[0039]

[0040] In formula (VI), R １４ 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. １５ represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. Each 'i' independently represents an integer from 0 to 3. 'n' is the average value, representing a number from 0 to 10.

[0041] 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, epoxy resins represented by the following general formula (VII) are preferred. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) where i=0 is available commercially.

[0042]

[0043] In formula (VII), R １６represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. Each 'i' independently represents an integer from 0 to 3. 'n' is the average value, representing a number from 0 to 10.

[0044] The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, epoxy resins obtained by glycidyl etherification of triphenylmethane-type phenolic resins such as novolac-type phenolic resins made from a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group are preferred, and epoxy resins represented by the following general formula (VIII) are more preferred. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and EPPN-502H (Nippon Kayaku Co., Ltd., trade name), in which i is 0 and k is 0, are commercially available.

[0045]

[0046] In formula (VIII), R １７ and R １８ represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical 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 represents a number from 0 to 10.

[0047] The copolymer 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 that uses compounds having a naphthol skeleton and compounds having a phenol skeleton as raw materials. For example, an epoxy resin obtained by glycidyl etherification of a novolac-type phenol resin using compounds having a naphthol skeleton and compounds having a phenol skeleton is preferred, and an epoxy resin represented by the following general formula (IX) is more preferred. Among the epoxy resins represented by the following general formula (IX), R ２１ NC-7300 (Nippon Kayaku Co., Ltd., trade name), in which the group is a methyl group, i is 1, j is 0, and k is 0, is available commercially.

[0048]

[0049] 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 independent integer from 0 to 3, j is an independent integer from 0 to 2, and k is an independent integer from 0 to 4. 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 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).

[0050]

[0051] 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.

[0052] As a copolymer epoxy resin, Epiclon HP-5000 (DIC Corporation, trade name), represented by the following general formula, is also preferred, as it is a methoxynaphthalene-cresolformaldehyde cocondensation epoxy resin containing the following two structural units in a random, alternating, or blocky order. In the following general formula, n and m are each average values, numbers from 0 to 10, and (n+m) represents a number from 0 to 10. Preferably, n and m are each average values, numbers from 1 to 9, and (n+m) represents a number from 2 to 10.

[0053]

[0054] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin made from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and a phenol resin synthesized from dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or derivatives thereof. For example, an epoxy resin obtained by glycidyl etherification of 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 dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or derivatives thereof is preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

[0055] Among the epoxy resins represented by the following general formula (X), i is 0 and R ３８ NC-3000S (Nippon Kayaku Co., Ltd., product name) is a hydrogen atom, i is 0, R ３８ Epoxy resin 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 Chemical & Material Co., Ltd., trade name), in which i is 0, j is 0, and k is 0, are commercially available.

[0056]

[0057] 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 of them may be the same or different. Each i is an independent integer from 0 to 3, each j is an independent integer from 0 to 2, each k is an independent integer from 0 to 4, and each l is an independent integer from 0 to 6. n is the average value, and each is an independent number from 0 to 10.

[0058] 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 R, this means that the number of each element included in the formula may be the same or different. ８ ~R ２１ and R ３７ ~R ４１ These can be the same or different. For example, R ９ and R １０ All of these 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.

[0059] In the above general formulas (II) to (XI), n is an average value, and it is preferable that each n 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 thermosetting 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.

[0060] The functional group equivalent of the thermosetting resin (epoxy equivalent in the case of epoxy resin) is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of the thermosetting resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

[0061] The softening point or melting point of the thermosetting resin 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 ease of handling during the preparation of the thermosetting resin composition, it is more preferably 50°C to 130°C.

[0062] The content of the thermosetting resin in the thermosetting 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.

[0063] (Curing agent) The thermosetting resin composition may contain a curing agent. The type of curing agent is not particularly limited and can be selected according to the type of thermosetting resin, the desired properties of the thermosetting resin composition, etc. When the thermosetting resin is an epoxy resin, examples of curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymer captan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. 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.

[0064] 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 an aldehyde compound 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; 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.

[0065] 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 (these are referred to as "specific phenol curing agents") is preferred from the viewpoint of reflow resistance. Specific phenol curing agents may be used individually or in combination of two or more types.

[0066] When the curing agent contains a specific phenol curing agent, from the viewpoint of fully exhibiting their performance, the content of the specific phenol curing agent is preferably 30% by mass or more of the total curing agent, and more preferably 50% by mass or more.

[0067] Examples of aralkyl-type phenolic resins include phenolic aralkyl resins synthesized from phenolic compounds with dimethoxyp-xylene, bis(methoxymethyl)biphenyl, etc., and naphthol aralkyl resins. Aalkyl-type phenolic resins may be further copolymerized with other phenolic resins. Examples of copolymerized aralkyl-type phenolic resins include copolymerized phenolic resins of benzaldehyde-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and copolymerized phenolic resins of novolac-type phenolic resin and aralkyl-type phenolic resin.

[0068] The aralkyl-type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds, and dimethoxyp-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof. For example, phenolic resins represented by the following general formulas (XII) to (XIV) are preferred.

[0069]

[0070] In equations (XII) to (XIV), R ２３R 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, and each of these may be identical 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 from 0 to 3, 'j' is an independent integer from 0 to 2, 'k' is an independent integer from 0 to 4, and 'p' is an independent integer from 0 to 4. 'n' is the average value, and each of these is an independent number from 0 to 10.

[0071] 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.

[0072] Among the phenolic resins represented by the above general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd., trade name), etc., in which i is 0 and k is 0, are available commercially.

[0073] Among the phenolic resins represented by the above general formula (XIV), SN-170 (Nippon Steel Chemical & Material Co., Ltd., product name) has j = 0, k = 0, and p = 0, and R has j = 0, k = 1. ２７ Products such as SN-395 (Nippon Steel Chemical & Material Co., Ltd., product name), in which the group is a hydroxyl group and p is 0, are commercially available.

[0074] The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XV) is preferred. Among the phenolic resins represented by the following general formula (XV), DPP (Shin Nippon Petrochemical Co., Ltd., trade name) in which i is 0 is available commercially.

[0075]

[0076] In formula (XV), R ２９ represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. Each 'i' independently represents an integer from 0 to 3. 'n' is the average value, representing a number from 0 to 10.

[0077] The triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a triphenylmethane skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferred.

[0078] Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (Meiwa Chemicals Co., Ltd., product name), in which i is 0 and k is 0, is available commercially.

[0079]

[0080] In formula (XVI), R ３０ and R ３１ represents 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, and each k is an independent integer from 0 to 4. n is the average value, a number from 0 to 10.

[0081] The copolymerized phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin is not particularly limited as long as it is a copolymerized phenol resin of a 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.

[0082] Among the phenolic resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., product name), in which i is 0, k is 0, and q is 0, is available commercially.

[0083]

[0084] In formula (XVII), R ３２ ~R ３４represents a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. Each i is independently an integer from 0 to 3, each k is independently an integer from 0 to 4, and each q is independently an integer from 0 to 5. l and m are average values and are each independently a number from 0 to 11. However, the sum of l and m is a number from 1 to 11.

[0085] The novolak 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 preferable.

[0086] Among the phenol resins represented by the following general formula (XVIII), when i is 0 and R ３５ are all hydrogen atoms, Tamanol 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP - 850N (Reizona Co., Ltd., trade name), etc. are commercially available.

[0087]

[0088] In formula (XVIII), R ３５ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. R ３６ represents a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. Each i independently represents an integer from 0 to 3. n is an average value and represents a number from 0 to 10. ]]

[0089] Regarding R ２２ to R ３６ described in the above general formulas (XII) to (XVIII), "they may all be the same or different from each other" means that, for example, all of the i R ２２ in formula (XII) may be the same or different from each other. The same applies to the other R ２３ to R ３６ ; that is, all of the respective numbers contained in the formula may be the same or different from each other. Also, regarding R ２２ to R ３６These can be the same or different. For example, R ２２ and R ２３ All of them may be the same or different, R ３０ and R ３１ All of them may be the same or different.

[0090] 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 will not become too high, the viscosity of the thermosetting resin composition during melt molding will also be low, and defects such as incomplete filling and deformation of bonding wires (gold wires connecting the element and leads) will be less likely to occur. The average n in one molecule is preferably set in the range of 0 to 4.

[0091] 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.

[0092] The softening point or melting point of the curing agent 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 thermosetting resin composition, it is more preferably 50°C to 130°C.

[0093] If the thermosetting resin composition contains a curing agent, the amount is preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, and even more preferably 50 to 60 parts by mass, per 100 parts by mass of the thermosetting resin. Furthermore, the equivalent ratio of the thermosetting 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 thermosetting resin (number of functional groups in the curing agent / number of functional groups in the thermosetting resin), is not particularly limited. In relation to minimizing the amount of 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.

[0094] (Curing accelerator) The thermosetting resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected according to the type of thermosetting resin, the desired properties of the thermosetting resin composition, etc.

[0095] From the viewpoint of curability and fluidity, it is preferable that the curing accelerator contains a phosphonium compound. Specifically, phosphonium compounds include tertiary phosphines such as triphenylphosphine, triphenylphosphine oxide, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl-alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and diazophenine. Compounds having intramolecular polarization, such as rumethane, obtained by adding a compound having a π bond; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodidephenol, 3-iodidephenol, 2-iodidephenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylpheno Compounds having intramolecular polarization obtained by reacting halogenated phenol compounds such as 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl, followed by a dehalogenation step; tetrasubstituted phosphoniums such as tetraphenylphosphonium, tetrasubstituted phosphoniums and tetrasubstituted borates such as tetra-p-tolylborate, which lack phenyl groups bonded to the boron atom;Examples include salts of tetrasubstituted phosphonium with an anion obtained by removing a proton from a phenol compound, and salts of tetrasubstituted phosphonium with an anion obtained by removing a proton from a carboxylic acid compound.

[0096] Among the phosphonium compounds mentioned above, the compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator) is preferred.

[0097]

[0098] In formula (I-1), R １ ~R ３ Each of these is independently a hydrocarbon group having 1 to 18 carbon atoms, and R １ ~R ３ Two or more of these may be bonded together to form a ring structure, R ４ ~R ７ Each of these is independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and R ４ ~R ７ Two or more of these may be joined together to form a ring structure.

[0099] R in general formula (I-1) １ ~R ３ The term "carbon hydrocarbon group having 1 to 18 carbon atoms" includes aliphatic hydrocarbon groups having 1 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms.

[0100] From the viewpoint of fluidity, the aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferably 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.

[0101] The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.

[0102] Examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl groups, as well as allyl and vinyl groups. Linear or branched aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy groups, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amino groups, and halogen atoms. Linear or branched aliphatic hydrocarbon groups may have two or more substituents, in which case the substituents may be the same or different. When a linear or branched aliphatic hydrocarbon group has substituents, it is preferable that the total number of carbon atoms in the aliphatic hydrocarbon group and the substituents is 1 to 18. From the viewpoint of curability, unsubstituted alkyl groups are preferred, unsubstituted alkyl groups having 1 to 8 carbon atoms are more preferred, and n-butyl groups, isobutyl groups, n-pentyl groups, n-hexyl groups, and n-octyl groups are even more preferred.

[0103] Specific examples of alicyclic hydrocarbons having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups. Alicyclic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups such as methyl, ethyl, butyl, and tert-butyl groups, alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy groups, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amino groups, and halogen atoms. Alicyclic hydrocarbon groups may have two or more substituents, and in that case, the substituents may be the same or different. When an alicyclic hydrocarbon group has substituents, it is preferable that the total number of carbon atoms in the alicyclic hydrocarbon group and the substituents is 3 to 18. When an alicyclic hydrocarbon group has substituents, the position of the substituents is not particularly limited. From the viewpoint of curability, unsubstituted cycloalkyl groups are preferred, unsubstituted cycloalkyl groups having 4 to 10 carbon atoms are more preferred, and cyclohexyl, cyclopentyl, and cycloheptyl groups are even more preferred.

[0104] Aromatic hydrocarbon groups having 6 to 18 carbon atoms are preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Aromatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups such as methyl, ethyl, butyl, and t-butyl groups; alkoxy groups such as methoxy, ethoxy, butoxy, and t-butoxy groups; aryl groups such as phenyl and naphthyl groups; hydroxyl groups; amino groups; and halogen atoms. Aromatic hydrocarbon groups may have two or more substituents, and in that case, the substituents may be the same or different. When an aromatic hydrocarbon group has substituents, the total number of carbon atoms in the aromatic hydrocarbon group and the substituents is preferably 6 to 18. When an aromatic hydrocarbon group has substituents, the position of the substituents is not particularly limited.

[0105] Specific examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, t-butylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, and t-butoxyphenyl groups. The substituents on these aromatic hydrocarbon groups may be in the ortho, meta, or para positions. From the viewpoint of fluidity, aryl groups having 6 to 12 carbon atoms unsubstituted or 6 to 12 carbon atoms with substituents are preferred, aryl groups having 6 to 10 carbon atoms unsubstituted or 6 to 10 carbon atoms with substituents are more preferred, and phenyl, p-tolyl, and p-methoxyphenyl groups are even more preferred.

[0106] R in general formula (I-1) １ ~R ３ The term "R" is listed as such. １ ~R ３ The phrase "Two or more of them may be bonded together to form a ring structure" means that R １ ~R ３ This refers to the case where two or three of them combine to form a single divalent or trivalent hydrocarbon group. １ ~R ３Examples of substituents that can bond with a phosphorus atom to form a cyclic structure include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene; alkenylene groups such as ethylene, propylene, and butylene; aralkylene groups such as methylenephenyl; and arylene groups such as phenylene, naphthylene, and anthracenylene. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

[0107] R in the above general formula (I-1) ４ ~R ７ The term "organic group having 1 to 18 carbon atoms" as described above means that it includes aliphatic hydrocarbon groups, aromatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, acyl groups, hydrocarbon oxycarbonyl groups, and acyloxy groups, which have 1 to 18 carbon atoms and may be substituted or unsubstituted.

[0108] Examples of the above aliphatic hydrocarbon group and aromatic hydrocarbon group include R １ ~R ３ The above examples include aliphatic hydrocarbon groups and aromatic hydrocarbon groups represented by [the given formula].

[0109] Examples of the above-mentioned aliphatic hydrocarbon oxy groups include oxy groups in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, t-butoxy, cyclopropyloxy, cyclohexyloxy, cyclopentyloxy, allyloxy, and vinyloxy groups, as well as those in which these aliphatic hydrocarbon oxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

[0110] Examples of the above-mentioned aromatic hydrocarbon oxy groups include oxy groups in which an oxygen atom is bonded to the above-mentioned aromatic hydrocarbon groups such as phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, and phenoxyphenoxy group, as well as those in which these aromatic hydrocarbon oxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

[0111] Examples of the acyl groups mentioned above include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethyl carbonyl group, butyryl group, cyclohexyl carbonyl group, and allyl carbonyl group, as well as aromatic hydrocarbon carbonyl groups such as phenyl carbonyl group and methylphenyl carbonyl group, and those in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

[0112] Examples of the hydrocarbon oxycarbonyl groups mentioned above include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, and cyclohexyloxycarbonyl group; aromatic hydrocarbon oxycarbonyl groups such as phenoxycarbonyl group and methylphenoxycarbonyl group; and those in which these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

[0113] Examples of the above-mentioned acyloxy groups 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 those in which these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

[0114] R in the above general formula (I-1) ４ ~R ７ The term "2 or more R" is listed as such. ４ ~R ７ The phrase "they may combine with each other to form a ring structure" means that 2 to 4 R ４ ~R ７ This means that they may bond together to form a single divalent to tetravalent organic group as a whole. ４ ~R ７ Examples include substituents that can form cyclic structures, such as alkylene groups like ethylene, propylene, butylene, pentylene, and hexylene; alkenylene groups like ethylene, propylene, and butylene; aralkylene groups like methylenephenyl; and arylene groups like phenylene, naphthylene, and anthracenylene; as well as their oxy or dioxy groups. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

[0115] R in the above general formula (I-1) ４ ~R ７ The choice is not particularly limited. For example, it is preferable to independently select 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. In particular, from the viewpoint of ease of raw material availability, an aryl group substituted with at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an unsubstituted or alkyl group, or an alkoxy group, or a linear or cyclic alkyl group is preferred. Examples of aryl groups that are unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, etc. Examples of linear or cyclic alkyl groups include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, t-butyl group, octyl group, cyclohexyl group, etc. From the viewpoint of curability, R ４ ~R ７ If all atoms are hydrogen atoms, or R ４ ~R ７It is preferable that at least one of the atoms is a hydroxyl group and the rest are all hydrogen atoms.

[0116] In general formula (I-1), more preferably, R １ ~R ３ Two or more of these are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, R ４ ~R ７ All are hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms. More preferably, R １ ~R ３ All of them are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, R ４ ~R ７ Either all of them are hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms.

[0117] From the viewpoint of rapid curing, the specific curing accelerator is preferably a compound represented by the following general formula (I-2).

[0118]

[0119] In formula (I-2), R １ ~R ３ Each of these is independently a hydrocarbon group having 1 to 18 carbon atoms, and R １ ~R ３ Two or more of these may be bonded together to form a ring structure, R ４ ~R ６ Each is independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ４ ~R ６ Two or more of these may be joined together to form a ring structure.

[0120] R in general formula (I-2) １ ~R ６ Specific examples are R in general formula (I-1). １ ~R ６ The specific examples are similar, and the preferred range is also similar.

[0121] Specific examples of specific hardening accelerators include the addition reaction products of triphenylphosphine and 1,4-benzoquinone, tri-n-butylphosphine and 1,4-benzoquinone, tricyclohexylphosphine and 1,4-benzoquinone, dicyclohexylphenylphosphine and 1,4-benzoquinone, cyclohexyldiphenylphosphine and 1,4-benzoquinone, triisobutylphosphine and 1,4-benzoquinone, and tricyclopentylphosphine and 1,4-benzoquinone.

[0122] Specific curing accelerators can be obtained, for example, as adducts of a tertiary phosphine compound and a quinone compound. Specific examples of tertiary phosphine compounds include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylphenyl)phosphine, tris(t-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, and tris(4-ethoxyphenyl)phosphine. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.

[0123] Examples of quinone compounds include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.

[0124] The thermosetting resin composition may contain curing accelerators other than phosphonium compounds. Other curing accelerators besides phosphonium compounds include, specifically, diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone. Examples include compounds having intramolecular polarization formed by adding compounds with π bonds, such as diazophenylmethane; cyclic amidinium compounds such as tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, tetraphenylborate salt of 2-ethyl-4-methylimidazole, and tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the aforementioned tertiary amine compounds; and ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide.

[0125] When a thermosetting 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 of the total curing accelerator, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0126] When a thermosetting resin composition contains a curing accelerator, the amount is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and even more preferably 10 to 25 parts by mass, per 100 parts by mass of the resin component. 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.

[0127] (Inorganic fillers) The thermosetting resin composition may contain inorganic fillers. In particular, when the thermosetting resin composition is used as a encapsulant for semiconductor packages, it is preferable to include inorganic fillers.

[0128] 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 inorganic fillers with flame retardant properties 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.

[0129] When a thermosetting resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 50% to 90% by mass of the total thermosetting resin composition, more preferably 55% to 90% by mass, and even more preferably 60% to 90% by mass. When the inorganic filler content is 0% by mass or more of the total thermosetting resin composition, the properties of the cured product, such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus, tend to improve further. When the inorganic filler content is 90% by mass or less of the total thermosetting resin composition, the increase in viscosity of the thermosetting resin composition is suppressed, and the fluidity tends to improve further, resulting in better moldability. When a thermosetting resin composition contains an inorganic filler, its content is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% to 90% by volume of the total thermosetting 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% by volume or more of the total thermosetting 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% by volume or less of the total thermosetting resin composition, the increase in viscosity of the thermosetting resin composition is suppressed, and the fluidity tends to improve, resulting in better moldability.

[0130] 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 40 μm, more preferably 1.0 μm to 30 μm, and even more preferably 5.0 μm to 25 μm. When the volume average particle size is 0.2 μm or more, the increase in viscosity of the resin composition for mold underfill tends to be further suppressed. When the volume average particle size is 40 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. In addition, as the inorganic filler, for example, an average primary particle size of 5 nm to 25 nm can be used, preferably an average primary particle size of 7 nm to 22 nm, and preferably an average primary particle size of 10 nm to 15 nm. The average primary particle size of inorganic fillers is determined by measuring the major axis of 100 randomly selected inorganic particles observed using a scanning electron microscope (SEM) and averaging the major axes of these 100 particles.

[0131] The volume-average particle size of inorganic fillers in a thermosetting resin composition or its cured product can be measured by known methods. For example, the inorganic filler can be extracted from the thermosetting 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 SEM) and performing three-dimensional structural analysis.

[0132] From the viewpoint of the fluidity of the thermosetting 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.

[0133] [Various Additives] In addition to the components described above, the thermosetting 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 thermosetting resin composition may also contain various additives known in the art, as needed, in addition to the additives exemplified below.

[0134] (Coupling Agents) If the thermosetting 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.

[0135] When the thermosetting 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.

[0136] (Ion Exchanger) The thermosetting resin composition may contain an ion exchanger. In particular, when the thermosetting resin composition is used as a molding material for sealing, it is preferable to include an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device equipped with the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, examples include hydrotalcite compounds and hydrated 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 these, hydrotalcite represented by the following general formula (A) is preferred.

[0137] Mg （１－Ｘ） AlＸ (OH) ２ (CO ３ ) Ｘ／２ ・mH ２ O ……(A) (0 < X ​​≤ 0.5, m is a positive number)

[0138] If the thermosetting resin composition contains an ion exchanger, there are no particular restrictions on its content as long as it is sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component.

[0139] (Release Agent) The thermosetting resin composition may contain a release agent from the viewpoint of obtaining good release properties from the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, 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 types.

[0140] When a thermosetting 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.

[0141] (Flame retardant) The thermosetting 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, metal hydroxides, etc. The flame retardant may be used alone or in combination of two or more types.

[0142] If the thermosetting 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.

[0143] (Colorants) The thermosetting resin composition may further contain colorants. 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.

[0144] (Stress Relief Agents) The thermosetting resin composition may contain stress relief agents such as silicone oil and silicone rubber particles. Including stress relief agents can further reduce package warping deformation and package cracking. Examples of stress relief agents include commonly used and known stress relief agents (flexible agents). Specifically, these include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based; 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 relief agent may be used alone, or two or more types may be used in combination. Among these, silicone-based stress relief agents are preferred. Examples of silicone-based stress relief agents include those having epoxy groups, those having amino groups, and those modified with polyether.

[0145] <Method for preparing thermosetting resin composition> The method for preparing the thermosetting resin composition is not particularly limited. A common method is to thoroughly mix predetermined amounts of components using a mixer or the like, then melt-knead them using a mixing roll, extruder or the like, cool them, and pulverize them. More specifically, for example, a method can be used in which predetermined amounts of the above-mentioned components are uniformly stirred and mixed, then kneaded using a kneader, roll, extruder or the like that has been preheated to 70°C to 140°C, then cooled, and pulverized.

[0146] The thermosetting resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25°C and atmospheric pressure). The shape of the thermosetting resin composition when it is solid is not particularly limited, and examples include powder, granules, and tablets. When the thermosetting 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.

[0147] <Sealing Material> The thermosetting resin composition of this disclosure can be used as a sealing material for sealing devices. That is, one embodiment of this disclosure is a sealing material using the thermosetting resin composition described above. The use of the thermosetting resin composition of this disclosure as a sealing material is intended as one application of the thermosetting resin composition of this disclosure, and the use of the thermosetting resin composition of this disclosure is not limited to sealing materials.

[0148] The encapsulant of this disclosure exhibits excellent tracking resistance. In particular, the encapsulant of this disclosure can exhibit excellent tracking resistance even when used as an encapsulant for so-called power semiconductors with a rated current of 1 A or more. Specifically, the encapsulant of this disclosure has tracking resistance exceeding 650 V when its tracking resistance is evaluated by the method described in the examples.

[0149] <Electronic Component Device> An electronic component device, which is one embodiment of the present disclosure, comprises an element and a cured product of the encapsulating material of the present disclosure described above. Examples of electronic component devices include those obtained by mounting elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and then encapsulating the element portion with a thermosetting resin composition. More specifically, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat) have 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, etc. using a thermosetting resin composition. Examples include general resin-encapsulated ICs such as Packages; TCPs (Tape Carrier Packages) having a structure in which elements connected to a tape carrier with bumps are encapsulated in a thermosetting 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 thermosetting resin composition; and BGAs (Ball Grid Arrays), CSPs (Chip Size Packages), MCPs (Multi Chip Packages), etc., having a structure in which elements are mounted on the surface of a support member having terminals for wiring board connection formed on the back surface, and after connecting the elements to the wiring formed on the support member by bumps or wire bonding, the elements are encapsulated in a thermosetting resin composition. Furthermore, thermosetting resin compositions can also be suitably used in printed circuit boards.

[0150] Methods for encapsulating electronic components using thermosetting resin compositions include low-pressure transfer molding, injection molding, and compression molding. Among these, low-pressure transfer molding is the most common.

[0151] The embodiments of this disclosure will be described in detail below with reference to examples, but the technical scope of this disclosure is not limited to these examples.

[0152] [Preparation of Thermosetting Resin Compositions] The thermosetting resin compositions of Example 1 and Comparative Examples 1 to 5 were prepared by mixing the following materials with 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.

[0153] (Epoxy resin) Epoxy resin 1: Epoxy equivalent 186, biphenyl-type epoxy resin Epoxy resin 2: Epoxy equivalent 282, biphenyl skeleton-containing aralkyl-type epoxy resin

[0154] (Hardening agent) Hardening agent 1: Hydroxyl group equivalent 156 g / eq, phenol novolac resin

[0155] (Curing accelerators) Curing accelerator 1: Addition reaction product of triphenylphosphine and 1,4-benzoquinone Curing accelerator 2: Triphenylphosphine oxide

[0156] (Coupling agent) Coupling agent 1: Silane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane)

[0157] (Release agent) Release agent 1: Carnauba wax

[0158] (Coloring agent) Coloring agent 1: Carbon black

[0159] (Ion exchanger) Ion exchanger 1: Hydrotalcite

[0160] (Additives) Additive 1: 2,4,6-tris[bis(methoxymethyl)]-1,3,5-triazine Additive 2: Glycouryl compound 1 Additive 3: Glycouryl compound 2 Additive 4: 3,5-diamino-1,2,4-triazole Additive 5: Triazole compound

[0161] (Inorganic fillers) Inorganic filler 1: Dry silica (average primary particle size: 12 nm) Inorganic filler 2: Fused silica (volume average particle size (D50): 20 μm)

[0162]

[0163] [Evaluation of Thermosetting Resin Compositions] The tracking resistance of the encapsulants prepared using the thermosetting resin compositions in Example 1 and Comparative Examples 1 to 5 was evaluated by the following tests. Unless otherwise specified, the encapsulants were molded using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Post-curing was also performed at 175°C for 5 hours as needed.

[0164] (1) Tracking resistance test: Using a flat plate test specimen and a platinum electrode, a voltage was applied while dropping a 0.1% by mass aqueous solution of ammonium chloride in accordance with IEC-60112:2003 4th edition, and the applied voltage (V: volts) at which tracking occurred in the test specimen was measured.

[0165] (2) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing material was molded under the above conditions and the flow distance (cm) was determined.

[0166] (3) Measurement of molding shrinkage rate The resin composition for molding was molded using a transfer molding machine under the conditions of a molding temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds. After curing at 175°C for 5 hours, a plate-shaped molded product (length 127 mm, width 12.7 mm, thickness 6.4 mm) was obtained. The molding shrinkage rate A (%) was calculated from the length D of the mold cavity at 25°C, which was measured in advance, and the length d of the molded product at room temperature (25°C) using the following formula: Molding shrinkage rate A (%) = ((D - d) / D) × 100

[0167] [Evaluation Results of Thermosetting Resin Compositions] The results of the above "(1) Tracking Resistance Test" (CTI test results), "(2) Spiral Flow", and "(3) Molding Shrinkage Rate Measurement" are shown in Table 2.

[0168]

[0169] As shown in Table 2, Example 1, which contains a nitrogen atom-containing compound with a nitrogen atom content of 67% by mass or more (3,5-diamino-1,2,4-triazole in this example), showed excellent tracking resistance. Furthermore, Example 1 exhibited a low molding shrinkage rate, demonstrating excellent dimensional stability. From the spiral flow results, it was revealed that Example 1, containing 3,5-diamino-1,2,4-triazole, not only had superior tracking resistance but also superior fluidity compared to Comparative Example 5.

[0170] Furthermore, all documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard had been specifically and individually noted as being incorporated by reference.

Claims

1. A thermosetting resin composition comprising a thermosetting resin and a nitrogen atom-containing compound having a nitrogen atom content ratio of 67% by mass or more, calculated by the following formula (1): Nitrogen atom content ratio = (Number of nitrogen atoms in the compound × 14) × 100 / (Molecular weight) ... (1) 2. The thermosetting resin composition according to claim 1, wherein the nitrogen atom-containing compound is a nitrogen-containing heterocyclic compound.

3. The thermosetting resin composition according to claim 1, wherein the nitrogen atom-containing compound is a compound having a triazole structure.

4. The thermosetting resin composition according to claim 1, wherein the nitrogen atom-containing compound is 3,5-diamino-1,2,4-triazole.

5. The thermosetting resin composition according to claim 1, wherein the nitrogen atom content ratio of the nitrogen atom-containing compound is 70% by mass or more.

6. The thermosetting resin composition according to claim 1, wherein the thermosetting resin comprises an epoxy resin.

7. The thermosetting resin composition according to claim 1, further comprising at least one selected from the group consisting of a curing agent, a curing accelerator, and an inorganic filler.

8. A sealing material comprising the thermosetting resin composition according to any one of claims 1 to 7.

9. An electronic component device comprising an element and a cured product of the sealing material according to claim 8 for sealing the element.

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