Resin composition for sealing, and electronic component device

Abstract

This resin composition for sealing includes an epoxy resin, a phenolic curing agent, a curing promoter, an ester compound having three or more phenolic hydroxyl groups, and an inorganic filler.

Description

Encapsulating resin composition and electronic component device

[0001] This disclosure relates to a resin composition for sealing and an electronic component device.

[0002] Epoxy resins are generally used as encapsulating resins for semiconductor devices because they offer superior moldability, adhesion, electrical properties, mechanical properties, and moisture resistance compared to other thermosetting resins. In recent years, the miniaturization of electronic devices and the high integration of semiconductor elements have led to increased complexity in the shapes of semiconductor elements. Therefore, encapsulating resin compositions used to encapsulate semiconductor elements require even higher fluidity than before. Furthermore, the recent thinning of bonding wires has made wire deformation more likely due to the flow of the encapsulating resin composition during encapsulation. From this perspective as well, high fluidity is required for encapsulating resin compositions (see, for example, Patent Documents 1 and 2).

[0003] International Publication No. 2019 / 131669, International Publication No. 2020 / 130098

[0004] However, increasing the fluidity of a encapsulating resin composition tends to decrease its curability, and generally, fluidity and curability are in a trade-off relationship. This disclosure has been made in view of the above-mentioned conventional circumstances, and aims to provide an encapsulating resin composition with excellent fluidity and curability, and an electronic component device using the same.

[0005] The specific means for achieving the above objectives are as follows: <1> A encapsulating resin composition comprising an epoxy resin, a phenolic curing agent, a curing accelerator, an ester compound having three or more phenolic hydroxyl groups, and an inorganic filler. <2> The encapsulating resin composition according to <1>, wherein the molar ratio of the ester compound to the curing accelerator is 0.1 or more. <3> The encapsulating resin composition according to <1> or <2>, wherein the curing accelerator is a compound containing a phosphorus element or an imidazole compound. <4> An electronic component device comprising an element and a cured product of the encapsulating resin composition according to any one of <1> to <3> for encapsulating the element.

[0006] According to one embodiment of the present disclosure, it is possible to provide a sealing resin composition with excellent fluidity and curability, and an electronic component device obtained using the same.

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

[0008] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that are not clearly distinguishable 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 by the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced by the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. When multiple types of the substance corresponding to each component are present in a 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, particles corresponding to 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 refers to the value for a mixture of those multiple types of particles present in the composition, unless otherwise specified.

[0009] In the notation of the groups (atomic groups) of the present disclosure, the notation that does not indicate substitution or non-substitution includes those having no substituents as well as those having substituents. In the present disclosure, the number of structural units represents an integer value for a single molecule, but represents a rational number that is an average value for an aggregate of multiple types of molecules. In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in the entire group. When the group has no substituents, it represents the number of carbon atoms forming the skeleton of the group. When the group has substituents, it represents the total number obtained by adding the number of carbon atoms in the substituents to the number of carbon atoms forming the skeleton of the group.

[0010] <Sealing resin composition> The sealing resin composition of the present disclosure contains an epoxy resin, a phenolic curing agent, a curing accelerator, an ester compound having three or more phenolic hydroxyl groups, and an inorganic filler. Hereinafter, the "ester compound having three or more phenolic hydroxyl groups" is also referred to as a "specific ester compound". By having the above configuration, the sealing resin composition is excellent in fluidity and curability. The reason is not clear, but it is speculated as follows.

[0011] The phenolic hydroxyl groups of the specific ester compound improve the affinity between the resin and the inorganic filler due to the interaction between the resin such as the epoxy resin and the phenolic curing agent and the inorganic filler, and a resin composition excellent in fluidity and curability can be obtained. From the viewpoint of promoting the interaction, the number of phenolic hydroxyl groups of the specific ester compound is three or more.

[0012] Hereinafter, each component constituting the sealing resin composition will be described. The sealing resin composition of the present disclosure contains an epoxy resin, a phenolic curing agent, a curing accelerator, a specific ester compound, and an inorganic filler, and may contain various additives such as a coupling agent, a stress reliever, a release agent, a colorant, a flame retardant, and an ion exchanger as necessary.

[0013] (Epoxy resin) The type of the epoxy resin is not particularly limited as long as it has an epoxy group in the molecule. Specific examples of the epoxy resin are described below, but the epoxy resin is not limited to these specific examples.

[0014] Specifically, at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. 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 phenolic compound with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde under an acidic catalyst and then epoxidizing it; triphenylmethane-type epoxy resins are obtained by epoxidizing a triphenylmethane-type phenolic resin obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst and then epoxidizing it; copolymer-type epoxy resins are obtained by epoxidizing a novolac resin obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst and then epoxidizing it; diphenylmethane is a diglycidyl ether such as bisphenol A or bisphenol F. Epoxy resins of various types; biphenyl-type epoxy resins, which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins, which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur atom-containing epoxy resins, which are diglycidyl ethers of bisphenol S, etc.; epoxy resins, which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins, which are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins, in which active hydrogen bonded to nitrogen atoms such as aniline, diaminodiphenylmethane, and isocyanuric acid is substituted with glycidyl groups; dicyclopentadiene-type epoxy resins, which are epoxidized co-condensation resins of dicyclopentadiene and phenolic compounds;Vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; Paraxylylene-modified epoxy resin which is a glycidyl ether of paraxylylene-modified phenol resin; Metaxylylene-modified epoxy resin which is a glycidyl ether of metaxylylene-modified phenol resin; Terpene-modified epoxy resin which is a glycidyl ether of terpene-modified phenol resin; Dicyclopentadiene-modified epoxy resin which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin which is a glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of polycyclic aromatic ring-modified phenol resin; Naphthalene-type epoxy resin which is a glycidyl ether of naphthalene ring-containing phenol resin; Halogenated phenol novolak-type epoxy resin; Hydroquinone-type epoxy resin; Trimethylolpropane-type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl-type epoxy resin obtained by epoxidizing an aralkyl-type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin; etc. are mentioned. Further, aminophenol-type epoxy resin which is a glycidyl ether of aminophenol etc. is also mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more kinds.;

[0015] Among the above epoxy resins, from the viewpoint of fluidity, it is preferable to contain a biphenyl-type epoxy resin. The proportion of the biphenyl-type epoxy resin in the whole epoxy resin is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.

[0016] 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 preferable.

[0017]

[0018] 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.

[0019] 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.

[0020]

[0021] 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.

[0022] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferred.

[0023]

[0024] 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.

[0025] 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.

[0026]

[0027] 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.

[0028] The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin. For example, an epoxy resin represented by the following general formula (VI) can be mentioned.

[0029]

[0030] In the 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, 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.

[0031] 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) can be mentioned.

[0032]

[0033] In the 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.

[0034] 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, an epoxy resin obtained by glycidyl etherifying a triphenylmethane type phenol resin obtained from an aromatic aldehyde compound and a phenolic compound is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable.

[0035]

[0036] In the formula (VIII), R １７ and R １８represents 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.

[0037] The copolymer epoxy resin obtained by epoxidizing a novolac resin from naphthol compounds, phenol compounds, and aldehyde compounds 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, epoxy resins represented by the following general formula (IX) can be mentioned.

[0038]

[0039] 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).

[0040]

[0041] Examples of epoxy resins represented by the above general formula (IX) include random copolymers containing l structural units and m structural units randomly, alternating copolymers containing them alternately, copolymers containing them regularly, and block copolymers containing them in a block-like manner. Any one of these types may be used alone or two or more types may be used in combination.

[0042] As a copolymer epoxy resin, Epiclon HP-5000 (DIC Corporation, trade name), which is a methoxynaphthalene-cresolformaldehyde cocondensation epoxy resin containing the following two structural units in a random, alternating, or blocky order, is also preferred. For example, an epoxy resin represented by the following general formula can be used. In the following general formula, n and m are each average values ​​and are numbers from 0 to 10, (n + m) is a number from 0 to 10, preferably n and m are each average values ​​and are numbers from 1 to 9, and (n + m) is a number from 2 to 10.

[0043]

[0044] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin made 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 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.

[0045]

[0046] 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 ４１ represents a monovalent organic group having 1 to 18 carbon atoms, and each of them may be identical 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 4. n is the average value, and each is an independent number from 0 to 10.

[0047] 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 all 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 monovalent organic group having 1 to 18 carbon atoms in general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

[0048] In the above general formulas (II) to (XI), n is an average value, and it is preferable that each is independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the sealing 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.

[0049] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of balancing various properties such as moldability, heat resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 40 g / eq to 1000 g / eq, more preferably 45 g / eq to 500 g / eq, and even more preferably 50 g / eq to 350 g / eq. The epoxy equivalent of the epoxy resin shall be the value measured by the method in accordance with JIS K 7236:2009.

[0050] The epoxy resin may be solid or liquid at 25°C. When the epoxy resin is solid at 25°C, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of balancing moldability and heat resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C. Furthermore, from the viewpoint of ease of handling during the manufacture of the sealing resin composition, the softening point or melting point of the epoxy resin is preferably 50°C to 130°C. In this disclosure, the softening point refers to the value measured by the ring-and-ball method of JIS K 7234:1986. In this disclosure, the melting point refers to the value measured by the visual method of JIS K 0064:1992.

[0051] The total content of epoxy resin in the sealing resin composition is preferably 0.5% to 60% by mass, more preferably 2% to 50% by mass, and even more preferably 3% to 45% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc.

[0052] (Curing agent) A single phenolic curing agent may be used alone, or two or more may be used in combination. In this disclosure, a curing agent is defined as a compound that has a structure capable of reacting with the epoxy resin contained in the encapsulating resin composition and curing the encapsulating resin composition. Compounds that are present in small amounts and contribute little to the curing reaction of the encapsulating resin composition are also considered to be included as curing agents.

[0053] Examples of phenolic curing agents include phenolic resins and polyhydric phenolic compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, these include polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde under an acidic catalyst; and phenolic resins synthesized from the above phenolic compounds with dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. Examples include aralkyl-type phenolic resins such as ol-aralkyl resins and naphthol-aralkyl resins; para-xylylene and / or meta-xylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used individually or in combination of two or more types.

[0054] 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 triphenylmethane-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.

[0055] 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.

[0056]

[0057] In equations (XII) to (XIV), R ２３ R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. ２２ , R ２４ , R ２５ and R ２８ R represents a monovalent organic group having 1 to 18 carbon atoms, 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.

[0058] From the viewpoint of adhesion to the lead frame and heat resistance of the sealing resin composition of this disclosure, the aralkyl type phenolic resin is preferably a phenolic resin represented by general formula (XIII). From the viewpoint of adhesion to the lead frame and heat resistance of the sealing resin composition of this disclosure, it is also preferable that i and k in general formula (XIII) are both 0.

[0059] 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) can be mentioned.

[0060]

[0061] 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.

[0062] The triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferred.

[0063]

[0064] 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.

[0065] The copolymerized phenol resin of a triphenylmethane-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.

[0066]

[0067] In formula (XVII), R ３２ ~R ３４ 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, each k is an independent integer from 0 to 4, and each q is an independent integer from 0 to 5. l and m are the average values, and each is an independent number from 1 to 11.

[0068] The novolac-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. For example, a phenolic resin represented by the following general formula (XVIIIII) is preferred.

[0069]

[0070] In formula (XVIII), R ３５ 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. ３６ 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.

[0071] In the above general formulas (XII) to (XVIII), R ２２ ~R ３６ The statement "they may all be the same or all different" refers, for example, to the i Rs in equation (XII). ２２ This means that all of them may be identical or mutually different. ２３ ~R ３６ Regarding this as well, it means that the number of each element included in the formula may all be the same or they may be different from each other. Also, R ２２ ~R ３６ These can be the same or different. For example, R ２２ and R ２３ All of them may be the same or different, R ３０ and R ３１All of them may be the same or different.

[0072] 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 sealing resin composition during melt molding will also be low, and filling defects, 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.

[0073] The hydroxyl equivalent of the phenolic curing agent is not particularly limited. From the viewpoint of balancing various properties such as moldability, heat resistance, and electrical reliability, it is preferably 10 g / eq to 1000 g / eq, and more preferably 30 g / eq to 500 g / eq. The hydroxyl equivalent of the phenolic curing agent refers to the value calculated based on the hydroxyl value measured in accordance with JIS K 0070:1992.

[0074] When the phenolic curing agent is solid at 25°C, its softening point or melting point is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the phenolic curing agent is preferably 40°C to 180°C. Furthermore, from the viewpoint of handling during the manufacture of the sealing resin composition, the softening point or melting point of the phenolic curing agent is preferably 50°C to 130°C.

[0075] The equivalent ratio of phenolic hydroxyl groups (active hydrogen) of the phenolic curing agent to the epoxy groups of the epoxy resin in the sealing resin composition (moles of phenolic hydroxyl groups (active hydrogen) of the phenolic curing agent / moles of epoxy groups of the epoxy resin) is not particularly limited, but for example it can be 0.5 to 1.2, 0.5 to 1.0, 0.55 to 0.9, or 0.6 to 0.8.

[0076] In addition to phenolic curing agents, other curing agents may be included. Examples of other curing agents include amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents.

[0077] When the curing agent contains other curing agents, from the viewpoint of fluidity, the content of the phenolic curing agent relative to the total mass of the curing agent is preferably 60% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, particularly preferably 90% to 100% by mass, and may be 100% by mass.

[0078] (Specific Ester Compounds) Specific ester compounds are ester compounds having three or more phenolic hydroxyl groups. Specific ester compounds may be used individually or in combination of two or more. The number of phenolic hydroxyl groups in a specific ester compound may be three to five.

[0079] The specific ester compound preferably includes a compound represented by the following formula (1).

[0080]

[0081] In formula (1), R represents an alkyl group, and n represents an integer from 3 to 5.

[0082] The alkyl group represented by R may be linear, branched, or cyclic, but it is preferably linear from the viewpoint of fluidity. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 3, from the viewpoint of fluidity.

[0083] In formula (1), n ​​is preferably 3 or 4, and more preferably 3. The bond position of the hydroxyl group attached to the phenyl group may be any of the following. When n is 3, the bond position of the hydroxyl group attached to the phenyl group may be at positions 2,3,4,2,3,5,2,3,6,2,4,5,2,4,6,3,4,5, or 3,4,6, and more preferably at positions 3,4,5. When the compound represented by formula (1) has a hydroxyl group at positions 3,4,5, this compound is a gallic acid ester. When n is 4, the bond position of the hydroxyl group attached to the phenyl group may be at positions 2,3,4,5,2,3,4,6,2,3,5,6.

[0084] Examples of compounds represented by formula (1) include methyl gallate, ethyl gallate, and propyl gallate.

[0085] From the viewpoint of moldability, the molecular weight of the specific ester compound is preferably 50 to 600, more preferably 100 to 550, and even more preferably 150 to 500.

[0086] From the viewpoint of moldability, the melting point of the specific ester compound is preferably 50°C to 250°C, more preferably 60°C to 240°C, and even more preferably 70°C to 230°C.

[0087] From the viewpoint of balancing fluidity and curability, the molar ratio of the specific ester compound to the curing accelerator (specific ester compound / curing accelerator) in the sealing resin composition may be 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1.0 or more. Furthermore, from the viewpoint of curability, the molar ratio (specific ester compound / curing accelerator) is preferably 10.0 or less, more preferably 9.0 or less, and even more preferably 8.0 or less.

[0088] (Curing Accelerator) The type of curing accelerator is not particularly limited and can be selected according to the type of epoxy resin, the desired properties of the encapsulating resin composition, etc. One type of curing accelerator may be used alone, or two or more types may be used in combination. Specific examples of curing accelerators are listed below, but the invention is not limited to these. Examples of curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and 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. Compounds having intramolecular polarization obtained by adding compounds with π bonds, such as zophenylmethane; 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 above 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;The following compounds containing the element phosphorus: primary phosphines such as ethylphosphine and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine, tributylphosphine, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl)phosphine, and other tertiary phosphines; phosphine compounds such as complexes of the above organophosphines with organoborons; and the above organophosphines or the above phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, Compounds having intramolecular polarization obtained by adding compounds having π bonds, such as quinone compounds like 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, and diazophenylmethane; and the organophosphine or the phosphine compound to 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-chlorophenol. Compounds having intramolecular polarization obtained by reacting halogenated phenol compounds such as phenol iodide, 3-iodide, 2-iodide, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl, followed by a dehalogenation step;Examples of tetrasubstituted phosphonium compounds include tetrasubstituted phosphoniums such as tetraphenylphosphonium, tetraphenylborate salts of tetrasubstituted phosphoniums such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetrasubstituted phosphoniums with phenolic compounds; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. Suitable curing accelerators include compounds containing phosphorus, with triphenylphosphine, tributylphosphine, quinone compound adducts of triphenylphosphine, and quinone compound adducts of tributylphosphine being more preferred. Imidazole compounds are also suitable curing accelerators.

[0089] The content of the curing accelerator is preferably 0.1 to 8 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 6 parts by mass, based on 100 parts by mass of the total amount of epoxy resin and curing agent. By setting the content of the curing accelerator within the above numerical range, the curing speed of the sealing resin composition of this disclosure becomes appropriate, and the manufacture of molded articles becomes easier.

[0090] (Inorganic Filler) The encapsulating resin composition of this disclosure contains an inorganic filler. The inclusion of an inorganic filler in the encapsulating resin composition tends to reduce its hygroscopicity and improve its strength in the cured state. When the encapsulating resin composition is used as an encapsulant for semiconductor packages, it is preferable that it contains an inorganic filler.

[0091] The inorganic materials constituting the inorganic filler are not particularly limited. Specific examples of inorganic materials include silica such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, boehmite, beryllia, magnesium oxide, zirconia, zircon, fossterite, steatite, spinel, mullite, titania, talc, clay, mica, and titanates. Inorganic fillers composed of inorganic materials with flame-retardant properties may also be used. Examples of inorganic materials with flame-retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxides, and zinc borate. One type of inorganic filler may be used alone, or two or more types may be used in combination.

[0092] The shape of the inorganic filler is not particularly limited and can be, for example, in powder, spherical, or fibrous form. From the viewpoint of fluidity during molding of the sealing resin composition and mold wear resistance, a spherical shape is preferred.

[0093] The average particle size of the inorganic filler is not particularly limited. From the viewpoint of balancing viscosity, packing properties, etc., of the sealing resin composition, the volume average particle size of the inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 40 μm, and even more preferably 0.5 μm to 30 μm. The volume average particle size of the inorganic filler can be measured as the volume average particle size (D50) using a laser diffraction scattering particle size distribution analyzer.

[0094] The particle size of the inorganic filler may be top-cut, top-cut at 100 μm or less, top-cut at 85 μm or less, top-cut at 75 μm or less, top-cut at 53 μm or less, top-cut at 20 μm or less, or top-cut at 10 μm or less. The top-cut particle size can be determined by the particle size distribution when the above volume-average particle size (D50) is measured.

[0095] When the encapsulating resin composition contains an inorganic filler, its content is not particularly limited. The inorganic filler content relative to the entire encapsulating resin composition is preferably 30% to 95% by mass, more preferably 40% to 95% by mass, and even more preferably 50% to 95% by mass. When the inorganic filler content is 30% by mass or more of the entire encapsulating 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 95% by mass or less of the entire encapsulating resin composition, the increase in viscosity of the encapsulating resin composition is suppressed, the fluidity improves further, and the moldability tends to be better.

[0096] The inorganic filler content relative to the total encapsulating resin composition is preferably 68% to 90% by volume, more preferably 70% to 88% by volume, and even more preferably 72% to 86% by volume. When the inorganic filler content is 68% or more by volume of the total encapsulating 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% or less by volume of the total encapsulating resin composition, the increase in viscosity of the encapsulating resin composition is suppressed, the fluidity improves further, and the moldability tends to be better.

[0097] (Various Additives) In addition to the components described above, the encapsulating resin composition of this disclosure may contain various additives such as coupling agents, stress relievers, mold release agents, colorants, flame retardants, and ion exchangers. Furthermore, the encapsulating resin composition of this disclosure may contain a siloxane compound having structural units with epoxy and alkoxy groups and a degree of polymerization of 2. In addition to the additives exemplified below, the encapsulating resin composition may contain various additives well known in the art as needed.

[0098] (Coupling Agent) The encapsulating resin composition of this disclosure may contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination.

[0099] Silane coupling agents are not particularly limited and include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, and the like.

[0100] Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylate isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0101] When the sealing resin composition contains a coupling agent, the content of the coupling agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and even more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the inorganic filler contained in the sealing resin composition, from the viewpoint of adhesion at the interface between the epoxy resin and the inorganic filler.

[0102] (Stress Relief Agent) The sealing resin composition of this disclosure may contain a stress relief agent such as silicone oil or silicone rubber particles. By including a stress relief agent in the sealing resin composition, the occurrence of package warping deformation and package cracks can be further reduced. Examples of stress relief agents include commonly used and known stress relief agents (flexible agents). Specifically, examples of stress relief agents 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 natural rubber (NR), acrylonitrile-butadiene copolymer (NBR), 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 relaxants include those containing epoxy groups, those containing amino groups, and those modified with polyethers. Triphenylphosphine oxide can also be used as a stress relaxant.

[0103] If the sealing resin composition contains a stress-relaxing agent, its content is preferably 5 to 60 parts by mass, and more preferably 10 to 55 parts by mass, per 100 parts by mass of epoxy resin contained in the sealing resin composition.

[0104] (Release Agent) The sealing resin composition of this disclosure may contain a release agent when a mold is used during molding, from the viewpoint of release from the mold. The release agent is not particularly limited, and conventionally known ones can be used. Examples of release agents 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. One type of release agent may be used alone, or two or more types may be used in combination.

[0105] When the sealing resin composition of this disclosure contains a release agent, the content of the release agent 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 epoxy resin contained in the sealing resin composition. When the amount of release agent is 0.01 parts by mass or more per 100 parts by mass of epoxy resin, sufficient release properties tend to be obtained. When it is 15 parts by mass or less, better release properties tend to be obtained.

[0106] (Colorants) The encapsulating resin compositions of this disclosure may 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 type of colorant may be used alone, or two or more types may be used in combination.

[0107] If the sealing resin composition contains a colorant, its content is preferably 0.01% to 5% by mass, and more preferably 0.05% to 4% by mass.

[0108] (Flame retardant) The sealing resin composition of this disclosure may contain a flame retardant. The flame retardant is not particularly limited and conventionally known ones can be used. Examples of flame retardants include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. One type of flame retardant may be used alone, or two or more types may be used in combination.

[0109] If the sealing resin composition of this disclosure contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. The amount of flame retardant is preferably 1 to 300 parts by mass, and more preferably 2 to 150 parts by mass, per 100 parts by mass of epoxy resin contained in the sealing resin composition.

[0110] (Ion Exchanger) The encapsulating resin composition of this disclosure may contain an ion exchanger. When the encapsulating resin composition is used as an encapsulant for a semiconductor package, it is preferable to include an inorganic ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device comprising the encapsulated element. 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. One type of ion exchanger may be used alone or two or more types may be used in combination. Specifically, an example of an ion exchanger is hydrotalcite represented by the following general formula (A).

[0111] Mg （１－Ｘ） Al Ｘ (OH) ２ (CO ３ ) Ｘ／２ ・mH ２ O...(A) (0 < X ​​≤ 0.5, m is a positive number)

[0112] If the sealing resin composition of this disclosure contains an ion exchanger, the amount thereof is not particularly limited as long as it is sufficient to capture ions such as halogen ions. The amount of ion exchanger is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of epoxy resin contained in the sealing resin composition.

[0113] (Physical properties of the sealing resin composition or its cured product) From the viewpoint of fluidity, the sealing resin composition of this disclosure preferably has a spiral flow (SF) of 100 cm or more, more preferably 105 cm or more, and even more preferably 110 cm or more, which can be determined by the following method. The upper limit of the spiral flow is not particularly limited and may be 200 cm or less.

[0114] Spiral flow measurement is performed by using a spiral flow measurement mold conforming to EMMI-1-66, and determining the flow distance when the sealing resin composition is molded in a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 180 seconds.

[0115] From the viewpoint of fluidity, the sealing resin composition of this disclosure preferably has a disk flow (DF) of 60 mm or more, more preferably 65 mm or more, and even more preferably 70 mm or more, determined by the following method. The upper limit of the disk flow is not particularly limited and may be 100 mm or less.

[0116] Disk flow (DF) is measured using a flat plate mold for disk flow measurement, which has an upper mold measuring 200 mm (W) x 200 mm (D) x 25 mm (H) and a lower mold measuring 200 mm (W) x 200 mm (D) x 15 mm (H). 5 g of sealing resin composition, weighed on a balance scale, is placed in the center of the lower mold heated to 175°C. After 5 seconds, the upper mold, also heated to 175°C, is closed, and compression molding is performed under conditions of a load of 78 N and a curing time of 180 seconds. The major diameter (mm) and minor diameter (mm) of the molded product are measured with calipers, and the average value (mm) is calculated.

[0117] From the viewpoint of curability, the heat hardness of the cured product of the sealing resin composition of this disclosure is preferably 60 or higher, more preferably 65 or higher, and even more preferably 70 or higher. Furthermore, there is no particular upper limit to the heat hardness, and it may be 100 or less, 95 or less, or 90 or less.

[0118] The thermal hardness of the cured product is measured immediately after molding using a Shore D hardness tester (for example, manufactured by Ueshima Seisakusho Co., Ltd.) by molding the sealing resin composition into a disc with a diameter of 50 mm and a thickness of 3 mm using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 180 seconds.

[0119] From the viewpoint of fluidity, the gel time of the sealing resin composition at 175°C is preferably 15 seconds or more, more preferably 18 seconds or more, even more preferably 20 seconds or more, and particularly preferably 21 seconds or more. From the viewpoint of curability, the gel time is preferably 80 seconds or less, more preferably 77 seconds or less, and even more preferably 74 seconds or less.

[0120] Gel time is measured from the time 0.5 g of the sealing resin composition is placed on a hot plate preheated to 175°C until the sealing resin composition loses its viscosity. It is preferable to heat the sealing resin composition while periodically stirring it with a spatula or the like. "Loss of viscosity of the sealing resin composition" refers to the phenomenon in which the sealing resin composition breaks or breaks when kneaded with a spatula or the like.

[0121] (Method for manufacturing the sealing resin composition) The method for manufacturing the sealing 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 the mixture using a mixing roll, extruder or the like, cool it, and pulverize it. 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 it.

[0122] The sealing resin composition is preferably solid at 25°C. When the sealing resin composition is solid at 25°C, the shape of the sealing resin composition is not particularly limited and can be in the form of powder, granules, tablets, etc. When the sealing resin composition is in tablet form, the dimensions and mass should be such that they are suitable for the molding conditions of the package, from the viewpoint of ease of handling.

[0123] (Uses of the encapsulating resin composition) The uses of the encapsulating resin composition of this disclosure are not particularly limited, and it can be used in various mounting technologies, for example, as an encapsulating material for electronic components and devices. Furthermore, the encapsulating resin composition of this disclosure can be used in various applications where it is desirable for the resin composition to have good fluidity and curability, such as resin molded articles for various modules, resin molded articles for motors, resin molded articles for automotive applications, and encapsulating materials for protective materials for electronic circuits.

[0124] <Electronic component device> The electronic component device of this disclosure comprises an element and a cured product of the above-mentioned sealing resin composition for sealing the element.

[0125] An electronic component device may include a support member for mounting elements. Examples of support members include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates. Among the above support members, lead frames are preferred from the viewpoint of adhesion to the cured product of the sealing resin composition. Elements may be mounted on one side of the lead frame.

[0126] Examples of elements found in electronic component devices include active elements such as silicon chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils.

[0127] Specific configurations of electronic component devices include, but are not limited to, the following: (1) General resin-encapsulated ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Lead Package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package), which have a structure in which elements are fixed on a lead frame, the terminal parts of the elements such as bonding pads are connected to the lead parts using wire bonding, bumps, etc., and then encapsulated using an encapsulating resin composition; (2) A TCP (Tape Carrier Package) having a structure in which elements connected to a tape carrier using bumps are sealed using an sealing resin composition; (3) A COB (Chip On Board) module, hybrid IC, multi-chip module, etc. having a structure in which elements connected to wiring formed on a support member using wire bonding, flip-chip bonding, solder, etc. are sealed using an sealing resin composition; (4) A BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), SiP (System in a Package) etc.

[0128] The method for encapsulating the element using the encapsulation resin composition is not particularly limited, and known methods can be applied. For example, low-pressure transfer molding is a common encapsulation method, but injection molding, compression molding, casting, etc., may also be used.

[0129] [Examples 1-3 and Comparative Examples 1-2] After pre-mixing (dry blending) the materials in the proportions (parts by mass) shown in Table 1, the mixture was kneaded for about 15 minutes using a twin-screw roller (roll surface temperature: about 80°C), cooled, and pulverized to produce a powdered sealing resin composition.

[0130] The details of the materials in Table 1 are as follows: • Epoxy resins: Epoxy resin A (naphthalene type, epoxy equivalent 250 g / eq), and epoxy resin B (biphenyl type, epoxy equivalent 192 g / eq)

[0131] • Curing agent: Curing agent A (phenol aralkyl resin, hydroxyl group equivalent 156 g / eq) • Curing accelerator: Curing accelerator A (adduct of triphenylphosphine and 1,4-benzoquinone)

[0132] • Specific ester compounds: methyl gallate, ethyl gallate, or propyl gallate • 2244THBP: 2,2',4,4'-tetrahydroxybenzophenone

[0133] • Release agent: Oxidized polyethylene wax • Coloring agent: Carbon black • Coupling agent: γ-glycidoxypropyltrimethoxysilane

[0134] • Inorganic filler: Spherical silica particles A with a volume-average particle diameter of 27.5 μm, and spherical silica particles B with a volume-average particle diameter of 0.5 μm.

[0135] <<Evaluation of the sealing resin compositions>> The properties of the sealing resin compositions prepared in Examples 1-3 and Comparative Examples 1-2 were measured and evaluated by the following method. The evaluation results are shown in Table 1.

[0136] <Measurement of Gel Time (GT)> For 3 g of the sealing resin composition, measurements were performed at a temperature of 180°C using a Curlastometer from JSR Trading Co., Ltd., and the time until the torque curve rose was defined as the gel time (seconds).

[0137] <Measurement of Spiral Flow (SF)> Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing resin composition was molded in a transfer molding machine under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance (cm) was determined.

[0138] <Measurement of Hot Hardness> The sealing resin composition was molded into a 50 mm diameter x 3 mm thickness disc using a transfer molding machine at a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Immediately after molding, the hot hardness (Shore D) of the test piece was measured using a Shore D hardness tester (manufactured by Ueshima Seisakusho Co., Ltd.).

[0139]

[0140] As shown in Table 1, the spiral flow of the encapsulating resin compositions of Examples 1 to 3 is higher than that of the encapsulating resin compositions of Comparative Examples 1 and 2. This indicates that the encapsulating resin compositions of Examples 1 to 3 have excellent fluidity. Furthermore, the thermal hardness of the cured products obtained from the encapsulating resin compositions of Examples 1 to 3 is about the same as that of the cured product obtained from the encapsulating resin composition of Comparative Example 1, indicating that the encapsulating resin compositions of Examples 1 to 3 maintain their curability without deterioration. Similarly, in the comparison between Comparative Example 2 and Examples 1 to 3, the thermal hardness of the cured products obtained from the encapsulating resin compositions of Examples 1 to 3 is about the same as that of the cured product obtained from the encapsulating resin composition of Comparative Example 2, indicating that the encapsulating resin compositions of Examples 1 to 3 maintain their curability without deterioration.

[0141] [Examples 4, 5 and Comparative Examples 3-5] The materials in the formulations (parts by mass) shown in Tables 2 and 3 were pre-mixed (dry blended), then kneaded in a twin-screw extruder with the internal temperature adjusted to 70°C to 100°C, cooled, and then pulverized to obtain a sealing resin composition.

[0142] The details of the materials in Tables 2 and 3 are as follows:

[0143] Epoxy resins: Epoxy resin B (biphenyl type, epoxy equivalent 192 g / eq), and epoxy resin C (biphenyl type, epoxy equivalent 172 g / eq)

[0144] • Curing agent: Curing agent B (triphenylmethane-type phenolic resin, hydroxyl group equivalent 104 g / eq) • Curing accelerator B: Adduct of tributylphosphine and 1,4-benzoquinone

[0145] • Specific ester compounds: Propyl gallate, 2,3-dihydroxynaphthalene

[0146] • Release agent: Oxidized polyethylene wax • Coloring agent: Carbon black • Coupling agent: γ-glycidoxypropyltrimethoxysilane

[0147] • Inorganic filler: Spherical alumina particles A with a volume-average particle diameter of 4.6 μm, and spherical alumina particles B with a volume-average particle diameter of 0.3 μm.

[0148] <<Evaluation of the encapsulating resin compositions>> The properties of the encapsulating resin compositions prepared in Examples 4 and 5 and Comparative Examples 3 to 5 were measured and evaluated by the following methods. The evaluation results are shown in Tables 2 and 3.

[0149] <Measurement of Gel Time (GT)> The gel time (seconds) was determined by measuring the time it took for the resin to lose its viscosity when 0.5 g of the sealing resin composition was placed on a hot plate preheated to 175°C.

[0150] <Measurement of Spiral Flow (SF)> Using a spiral flow measurement mold conforming to EMMI-1-66, the sealing resin composition was molded in a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 180 seconds, and the flow distance (cm) was determined.

[0151] <Measurement of Disc Flow (DF)> Using a disc flow measuring flat mold having an upper mold of 200 mm (W) x 200 mm (D) x 25 mm (H) and a lower mold of 200 mm (W) x 200 mm (D) x 15 mm (H), 5 g of sealing resin composition, weighed on a balance scale, was placed in the center of the lower mold heated to 175°C. After 5 seconds, the upper mold, also heated to 175°C, was closed and compression molded under conditions of a load of 78 N and a curing time of 180 seconds. The major diameter (mm) and minor diameter (mm) of the molded product were measured with calipers, and the average value (mm) was defined as the disc flow.

[0152] <Measurement of Hot Hardness> The sealing resin composition was molded into a 50 mm diameter x 3 mm thickness disc using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 180 seconds. Immediately after molding, the hot hardness (Shore D) of the test piece was measured using a Shore D hardness tester (manufactured by Ueshima Seisakusho Co., Ltd.).

[0153]

[0154]

[0155] From the evaluation results in Table 2, Comparative Example 4, which used the same mass of 2,3-dihydroxynaphthalene instead of gallic acid ester, and Comparative Example 3, which did not contain gallic acid ester, both showed lower spiral flow and disc flow values ​​than Example 4. From this, it can be seen that the encapsulating resin composition of Example 4 has superior fluidity compared to Comparative Examples 3 and 4. Furthermore, the thermal hardness of the cured product obtained from the encapsulating resin composition of Example 4 was about the same as that of the cured products obtained from the encapsulating resin compositions of Comparative Examples 3 and 4, indicating that the encapsulating resin composition of Example 4 maintained its curability without deterioration.

[0156] From the evaluation results in Table 3, Comparative Example 5, which used the same amount of 2,3-dihydroxynaphthalene instead of gallic acid ester, and Comparative Example 3, which did not contain gallic acid ester, both showed lower spiral flow and disc flow values ​​than Example 5. From this, it can be seen that the encapsulating resin composition of Example 5 has superior fluidity compared to Comparative Examples 3 and 5. Furthermore, the thermal hardness of the cured product obtained from the encapsulating resin composition of Example 5 was about the same as that of the cured products obtained from the encapsulating resin compositions of Comparative Examples 3 and 5, indicating that the encapsulating resin composition of Example 5 maintained its curability without deterioration.

[0157] The disclosure of Japanese Patent Application No. 2024-233019 is incorporated in its entirety by reference. All documents, patent applications, and technical standards in this disclosure 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 encapsulating resin composition comprising an epoxy resin, a phenolic curing agent, a curing accelerator, an ester compound having three or more phenolic hydroxyl groups, and an inorganic filler.

2. The encapsulating resin composition according to claim 1, wherein the molar ratio of the ester compound to the curing accelerator is 0.1 or more.

3. The encapsulating resin composition according to claim 1 or claim 2, wherein the curing accelerator is a compound containing a phosphorus element or an imidazole compound.

4. An electronic component device comprising an element and a cured product of the sealing resin composition according to claim 1 or claim 2 for sealing the element.

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