Resin composition for encapsulating semiconductor, and semiconductor device

Abstract

The semiconductor sealing resin composition of the present invention contains an epoxy resin (A), a curing agent (B) comprising a phenolic resin (B1) and an active ester resin (B2), and a curing accelerator (C). The active ester resin (B2) has a structure represented by general formula (1), and the curing accelerator (C) contains one or more of the following selected from the group consisting of tetraphenylphosphonium-4,4'-sulfonyl diphenol salt, tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate, and 4-hydroxy-2-(triphenylphosphonium)phenol salt.

Description

[Technical Field]

[0001] This invention relates to a resin composition for semiconductor sealing and a semiconductor device. [Previous Technology]

[0002] As a material for sealing semiconductor packages, a thermosetting resin composition (sealing resin composition) is known.

[0003] Patent documents 1 and 2 disclose a sealing resin composition containing epoxy resin, an active ester compound as a hardener, and an inorganic filler material having a specified average particle size.

[0004] Patent Document 3 discloses a sealing resin composition containing an epoxy resin and an active ester compound as a curing agent, wherein the epoxy resin includes polyfunctional epoxy resins and difunctional epoxy resins. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2020 / 065872 [Patent Document 2] International Publication No. 2020 / 065873 [Patent Document 3] International Publication No. 2020 / 066856 [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] However, in the conventional sealing resin compositions described in Patent Documents 1-3, the shrinkage rate during molding is high and the product yield is low, resulting in low mechanical strength of the sealing material and room for improvement in dielectric properties. [Technical Means for Solving the Problem]

[0008] The inventors have discovered that by using both phenolic resin and reactive ester resin as curing agents and employing a resin composition for semiconductor sealing containing a prescribed curing accelerator, the above-mentioned problems can be solved, thereby completing the present invention. That is, the present invention can be described as follows.

[0009] [1] A resin composition for semiconductor sealing, comprising: (A) an epoxy resin; (B) a curing agent; and (C) a curing accelerator, wherein the curing agent (B) comprises a phenolic resin (B1) and an active ester resin (B2), and the active ester resin (B2) has a structure represented by general formula (1), (in general formula (1), A is a substituted or unsubstituted aryl group linked by an aliphatic cyclic hydrocarbon group, Ar' is a substituted or unsubstituted aryl group, and k is the average value of the repeating unit, in the range of 0.25 to 3.5, In general formula (1), B is a structure represented by general formula (B), (in general formula (B), Ar is a substituted or unsubstituted aryl group, Y is a single bond, a substituted or unsubstituted linear alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a thioether group, or a ternary group. n is an integer from 0 to 4.) The curing accelerator (C) contains one or more of the following groups selected from the group consisting of tetraphenylphosphonium-4,4'-sulfonyl diphenol salt, tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate, and 4-hydroxy-2-(triphenylphosphonium)phenol salt. [2] The semiconductor sealing resin composition as in [1], wherein, The structure represented by the aforementioned general formula (B) is selected from at least one of the general formulas (B-1) to (B-6). (In general formulas (B-1) to (B-6), R1 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, R2 is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a phenyl group, X is any one of a straight-chain extended alkyl group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a thioether group, or a ternary group, n is an integer from 0 to 4, and p is an integer from 1 to 4.) [3] The semiconductor sealing resin composition as in [1] or [2], wherein, in the aforementioned general formula (1), A has a structure represented by general formula (A). (In general formula (A), R 3 is independently any one of hydrogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, phenyl group, aralkyl group, l is 0 or 1, m is an integer greater than or equal to 1) [4] A semiconductor sealing resin composition of any one of [1] to [3], wherein the ratio of the content of phenolic resin (B1) to the content of active ester resin (B2) is 25:75 to 75:25. [5] A semiconductor sealing resin composition of any one of [1] to [4] further contains a coupling agent (D). [6] A semiconductor sealing resin composition of [5], wherein the coupling agent (D) is a secondary aminosilane coupling agent. [7] A semiconductor sealing resin composition of any one of [1] to [6], wherein at least one of epoxy resin (A) and phenolic resin (B1) has a biphenyl aralkyl structure.[8] A semiconductor sealing resin composition of any one of [1] to [7], wherein the phenolic resin (B1) has a biphenyl aralkyl structure. [9] A semiconductor sealing resin composition of any one of [1] to [8], wherein the epoxy resin (A) contains at least one selected from biphenyl aralkyl type resins and dicyclopentadiene type resins.

[10] A semiconductor sealing resin composition of any one of [1] to [9] further contains polysiloxane oil (E).

[11] A semiconductor sealing resin composition of any one of [1] to

[10] further contains an inorganic filler (F).

[12] A semiconductor sealing resin composition of

[11] , wherein the inorganic filler (F) is at least one selected from silicon dioxide, alumina, talc, titanium dioxide, silicon nitride, and aluminum nitride.

[13] A semiconductor sealing resin composition of any one of [1] to

[12] , wherein the gel time of the semiconductor sealing resin composition is 50 seconds or more and 80 seconds or less.

[14] A semiconductor device comprising: a semiconductor element; and a sealing material composed of a hardened form of a semiconductor sealing resin composition of any one of [1] to

[13] , which seals the aforementioned semiconductor element. [Effects of the Invention].

[0010] The semiconductor sealing resin composition of the present invention exhibits low shrinkage during molding and excellent product yield, resulting in excellent mechanical strength and dielectric properties in the cured product obtained from the composition. In other words, the semiconductor sealing resin composition of the present invention achieves an excellent balance of these properties.

Implementation Method

[0012] Hereinafter, embodiments of the present invention will be described using drawings. Furthermore, in all the drawings, the same symbols are used to denote the same constituent elements, and descriptions are omitted where appropriate. Also, unless otherwise specified, "~" indicates "above" to "below".

[0013] The semiconductor sealing resin composition of this embodiment contains epoxy resin (A), a curing agent (B), and a curing accelerator (C). Hereinafter, the components contained in the semiconductor sealing resin composition of this embodiment (hereinafter also referred to as the sealing resin composition) will be described.

[0014] [Epoxy Resin (A)] Epoxy resin (A) is a compound having two or more epoxy groups in one molecule, and can be any of monomers, oligomers and polymers.

[0015] Specifically, epoxy resin (A) is selected from crystalline epoxy resins such as biphenyl-type epoxy resin, bisphenol-type epoxy resin, and zirconia-type epoxy resin; phenolic varnish-type epoxy resins such as phenolic varnish-type epoxy resin and cresolic varnish-type epoxy resin; multifunctional epoxy resins such as triphenol-methane-type epoxy resin and alkyl-modified triphenol-methane-type epoxy resin; phenolic aralkyl-type epoxy resin containing a phenyl skeleton; and epoxy resin containing biphenyl groups. e) One or more of the following groups: phenol aralkyl type epoxy resins, such as phenol aralkyl type epoxy resins; naphthol type epoxy resins, such as dihydroxynaphthalene type epoxy resins and epoxy resins obtained by etherifying dihydroxynaphthalene dimers with epoxypropyl ether; trichloroisocyanurate, monoallyldichloropropyl trichloroisocyanurate, and other epoxy resins containing trichloroisocyanurate cores; and dicyclopentadiene-modified phenol type epoxy resins.

[0016] From the viewpoint of the effectiveness of the present invention, epoxy resin (A) is preferably selected from one or more of the group consisting of triphenylmethane type epoxy resin, biphenyl aryl type polyfunctional epoxy resin, o-cresol type difunctional epoxy resin, biphenyl type difunctional epoxy resin, bisphenol type difunctional epoxy resin, and dicyclopentadiene type difunctional epoxy resin. It is more preferred that epoxy resin (A) is a biphenyl aryl type polyfunctional epoxy resin or a dicyclopentadiene type difunctional epoxy resin.

[0017] From the viewpoint of obtaining suitable flowability during molding to improve filling or formability, the content of epoxy resin (A) in the sealing resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, relative to the total sealing resin composition. Furthermore, from the viewpoint of improving the reliability of the device obtained using the sealing resin composition, the content of epoxy resin (A) in the sealing resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, relative to the total sealing resin composition.

[0018] [Curing agent (B)] In this embodiment, the curing agent (B) contains phenolic resin (B1) and reactive ester resin (B2).

[0019] (Phenolic resin (B1)) As phenolic resin (B1), a resin commonly used in sealing resin compositions can be used within the scope of exerting the effects of the present invention.

[0020] Phenolic resins (B1) include, for example, phenolic varnish resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, and dihydroxynaphthalene with formaldehyde or ketones under an acidic catalyst, such as phenolic aralkyl resins with a biphenyl skeleton synthesized from the above phenols and dimethoxy-p-xylene or bis(methoxymethyl)biphenyl, phenolic aralkyl resins with a biphenyl skeleton, and phenolic resins with a triphenylmethane skeleton. These can be used alone or in combination of two or more.

[0021] In this embodiment, from the viewpoint of the effects of the present invention, it is preferable that the phenolic resin (B1) has a biphenyl aralkyl structure; specifically, it is preferable that the phenolic aralkyl resin has a biphenyl backbone. Phenolic resins having a biphenyl aralkyl structure have low moisture absorption, low elasticity, and excellent reliability. In this embodiment, it is preferable that one or both of the epoxy resin (A) and the phenolic resin (B1) have a biphenyl aralkyl structure.

[0022] (Active ester resin (B2)) The active ester resin (B2) can be a resin having a structure represented by the following general formula (1).

[0023]

[0024] In formula (1), "B" is the structure represented by formula (B).

[0025]

[0026] In formula (B), Ar is a substituted or unsubstituted aryl group. Examples of substituents for the substituted aryl group include alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, phenyl groups, and aralkyl groups. Y is a single bond, a substituted or unsubstituted linear aryl group with 1 to 6 carbon atoms, a substituted or unsubstituted cyclic aryl group with 3 to 6 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a thioether group, or a ternary group. Examples of substituents for the aforementioned groups include alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, phenyl groups, and aralkyl groups. Preferably, Y is a single bond, a methylene group, a -CH(CH3)2- group, an ether bond, a substituted cycloalkylene group, or a substituted 9,9-fluorenylene group. n is an integer from 0 to 4, preferably 0 or 1. Specifically, B is a structure represented by the following general formula (B1) or the following general formula (B2).

[0027]

[0028] In the above general formula (B1) and the above general formula (B2), Ar and Y are synonyms with general formula (B).

[0029] A is a substituted or unsubstituted aryl group linked by an aliphatic cyclic hydrocarbon group, Ar' is a substituted or unsubstituted aryl group, and k is the average value of the repeating unit, in the range of 0.25 to 3.5.

[0030] The semiconductor sealing resin composition of this embodiment contains phenolic resin (B1) and a specific active ester resin (B2), which can produce a hardened material (sealing material) with low shrinkage during molding and excellent product yield, as well as excellent mechanical strength and low dielectric loss tangent.

[0031] The active ester resin (B2) used in the semiconductor sealing resin composition of this embodiment has active ester groups represented by formula (B). In the curing reaction between epoxy resin (A) and active ester resin (B2), the active ester groups of active ester resin (B2) react with the epoxy groups of epoxy resin to generate secondary hydroxyl groups. These secondary hydroxyl groups are blocked by the ester residues of active ester resin (B2). Therefore, the dielectric loss tangent of the cured material is reduced.

[0032] In one embodiment, it is preferable that the structure represented by the above formula (B) is selected from at least one of the following formulas (B-1) to (B-6).

[0033]

[0034] In formulas (B-1) to (B-6), R1 is independently any one of hydrogen atom, alkyl group with 1 to 4 carbon atoms, alkoxy group with 1 to 4 carbon atoms, phenyl group, and aralkyl group, respectively; R2 is independently any one of alkyl group with 1 to 4 carbon atoms, alkoxy group with 1 to 4 carbon atoms, and phenyl group, respectively; X is any one of straight-chain extended alkyl group with 2 to 6 carbon atoms, ether bond, carbonyl group, carbonyloxy group, thioether group, and uryl group; n is an integer from 0 to 4; and p is an integer from 1 to 4.

[0035] The structures represented by formulas (B-1) to (B-6) above are all highly oriented structures. Therefore, when using an active ester resin (B2) containing such a structure, the cured resin composition obtained has a low dielectric constant and a low dielectric loss tangent, and excellent adhesion to metals. Therefore, it can be used as a semiconductor sealing material. Among these, from the viewpoint of low dielectric constant and low dielectric loss tangent, an active ester resin (B2) having a structure represented by formulas (B-2), (B-3), or (B-5) is preferred. Furthermore, an active ester resin (B2) having a structure in formula (B-2) where n is 0, a structure in formula (B-3) where X is an ether bond, or a structure in formula (B-5) where the two carbonyl groups are located at the 4,4'-position is preferred. Also, it is preferred that all R1 in each formula is a hydrogen atom.

[0036] In formula (1), "Ar'" is an aryl group, such as phenyl, o-tolyl, m-tolyl, p-tolyl, 3,5-dimethyll, o-biphenyl, m-biphenyl, p-biphenyl, 2-benzylphenyl, 4-benzylphenyl, 4-(α-isopropylphenyl)phenyl, 1-naphthyl, 2-naphthyl, etc. Among them, 1-naphthyl or 2-naphthyl is preferred, especially in terms of obtaining a hardened material with low dielectric constant and low dielectric loss tangent.

[0037] In this embodiment, "A" in the active ester resin (B2) represented by formula (1) is a substituted or unsubstituted aryl group linked by an aliphatic cyclic hydrocarbon group. For example, such an aryl group can be described as a structure obtained by reacting an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule with a phenolic compound through a superaddition reaction.

[0038] Examples of unsaturated aliphatic cyclic hydrocarbon compounds containing two double bonds in one molecule include dicyclopentadiene, polymers of cyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norcamphene, and limonene. These compounds can be used individually or in combination of two or more. Among these, dicyclopentadiene is preferred in terms of obtaining a hardened product with excellent heat resistance. Furthermore, since dicyclopentadiene is contained in petroleum distillates, industrial dicyclopentadiene sometimes contains polymers of cyclopentadiene, other aliphatic or aromatic diene compounds, etc., as impurities. However, considering heat resistance, hardening properties, and formability, products with a dicyclopentadiene purity of 90% by mass or higher are preferred.

[0039] On the other hand, the aforementioned phenolic compounds include, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthol, 2,3-dihydroxynaphthol, 2,6-dihydroxynaphthol, and 2,7-dihydroxynaphthol, which can be used individually or in combination of two or more types. Among these, phenol is preferred in terms of becoming an active ester resin (B2) with high curability and excellent dielectric properties in the cured product.

[0040] In a preferred embodiment, the "A" in the active ester resin (B2) represented by formula (1) has a structure represented by formula (A). Among the resin compositions containing the active ester resin (B2) with the following structure of "A" in formula (1), the cured product has a low dielectric constant, a low dielectric loss tangent, and excellent adhesion to inserts.

[0041]

[0042] In formula (A), R3 is independently any one of hydrogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, phenyl group, aralkyl group, l is 0 or 1, and m is an integer greater than or equal to 1.

[0043] Among the active ester curing agents represented by formula (1), the resin represented by formula (1-1), formula (1-2) and formula (1-3) can be cited as a more preferred substance, and the resin represented by formula (1-3) can be cited as an especially preferred substance.

[0044]

[0045] In formula (1-1), R1 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; Z is a phenyl group, a naphthyl group, or a phenyl or naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on an aromatic core; l is 0 or 1; and k is the average of the repeating units, which is 0.25 to 3.5.

[0046]

[0047] In formula (1-2), R1 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; Z is a phenyl group, a naphthyl group, or a phenyl or naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on an aromatic core; l is 0 or 1; and k is the average of the repeating units, which is 0.25 to 3.5.

[0048]

[0049] In formula (1-3), R1 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; Z is a phenyl group, a naphthyl group, or a phenyl or naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on an aromatic core; l is 0 or 1; and k is the average of the repeating units, which is 0.25 to 3.5.

[0050] The active ester resin (B2) used in this invention can be manufactured by a known method of reacting a phenolic compound (a), a dicarboxylic acid containing an aromatic nucleus or its halide (b), and an aromatic monohydroxy compound (c), wherein the phenolic compound (a) has a structure formed by multi-nodular aryl groups having phenolic hydroxyl groups via aliphatic cyclic hydrocarbon groups.

[0051] The reaction ratio of the above-mentioned phenolic compound (a), the dicarboxylic acid or its halide containing an aromatic core (b), and the aromatic monohydroxy compound (c) can be appropriately adjusted according to the desired molecular design. In terms of obtaining a more curable active ester resin (B2), it is preferable to use each raw material in a ratio where the phenolic hydroxyl group of the aforementioned phenolic compound (a) is in the range of 0.25 to 0.90 mol and the hydroxyl group of the aforementioned aromatic monohydroxy compound (c) is in the range of 0.10 to 0.75 mol, relative to a total of 1 mol of carboxyl or halogenated acetic acid group contained in the aforementioned dicarboxylic acid or its halide (b). It is even preferable to use each raw material in a ratio where the phenolic hydroxyl group of the aforementioned phenolic compound (a) is in the range of 0.50 to 0.75 mol and the hydroxyl group of the aforementioned aromatic monohydroxy compound (c) is in the range of 0.25 to 0.50 mol.

[0052] Furthermore, when the functional group equivalent of the active ester resin (B2) is taken as the total number of aryl carbonyl groups and phenolic hydroxyl groups present in the resin structure as the number of functional groups of the resin, in terms of excellent curability and obtaining a cured product with low dielectric constant and dielectric loss tangent, the range of 200 g / eq or more and 230 g / eq or less is preferred, and the range of 210 g / eq or more and 220 g / eq or less is even more preferred.

[0053] The curing agent (B) composition of this embodiment contains phenolic resin (B1) and reactive ester resin (B2). Therefore, the semiconductor sealing resin composition of this embodiment has low shrinkage during molding and excellent product yield, resulting in excellent mechanical strength and low dielectric loss tangent in the cured product obtained from this composition.

[0054] In this embodiment, from the viewpoint of the effect of the present invention, the equivalent ratio of hardener (B) to epoxy resin (A) (hardener (B) / epoxy resin (A)) can be set to 0.50 to 1.00, preferably 0.52 to 0.95, more preferably 0.55 to 0.90, and especially preferably 0.60 to 0.80.

[0055] In this embodiment, the equivalent ratio of the reactive ester resin (B2) to the epoxy resin (A) (reactive ester resin (B2) / epoxy resin (A)) can be set to 0.10 to 0.60, preferably 0.12 to 0.50, more preferably 0.15 to 0.47, and particularly preferably 0.17 to 0.45. Therefore, the resin composition for semiconductor sealing in this embodiment exhibits excellent curability, resulting in lower shrinkage during molding and better product yield. Consequently, the cured product obtained from this composition exhibits superior mechanical strength and lower dielectric loss tangent. If the aforementioned equivalent ratio (B2 / A) exceeds the upper limit, the hydroxyl groups generated during epoxy ring opening are easily capped with the reactive ester, thus reducing the dielectric loss tangent. However, as in this embodiment, if the upper limit of the aforementioned equivalent ratio (B2 / A) is exceeded in the curing agent (B) that combines phenolic curing agent (B1) and reactive ester resin (B2), the phenolic hydroxyl groups of the phenolic curing agent (B1) react with the reactive ester of the reactive ester resin (B2), affecting the curing of epoxy resin (A). This results in uneven curing properties (spiral flow, gel time, etc.), reduced heat resistance (Tg, etc.) and mechanical properties (flexural strength, flexural modulus, etc.), and makes it difficult to control homogeneous dielectric properties (homogeneity of dielectric properties within the cured material).

[0056] In this embodiment, from the viewpoint of the effect of the present invention, the equivalent ratio of phenolic resin (B1) to epoxy resin (A) (phenolic resin (B1) / epoxy resin (A)) can be set to 0.10 to 0.70, preferably 0.15 to 0.65, more preferably 0.18 to 0.60, and particularly preferably 0.20 to 0.55.

[0057] From the viewpoint of the effects of the present invention, in the curing agent (B), the ratio of the content (parts by weight) of phenolic resin (B1) to the content (parts by weight) of active ester resin (B2) can be set to 25:75 to 75:25, preferably 30:70 to 70:30.

[0058] In the resin composition of this embodiment, regarding the amount of curing agent (B) containing phenolic resin (B1) and reactive ester resin (B2) and epoxy resin (A) blended, in order to obtain a cured product with excellent curability, low dielectric constant and low dielectric loss tangent, it is preferable that the epoxy groups in the epoxy resin are in a ratio of 0.8 to 1.2 equivalents relative to the total equivalent of the reactive groups in the curing agent (B). Here, the reactive groups in the curing agent (B) refer to the aryl carbonyl groups and phenolic hydroxyl groups present in the resin structure.

[0059] In the composition of this embodiment, the curing agent (B) is used in an amount of 0.2% by mass or more and 15% by mass or less relative to the total amount of the sealing resin composition, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1.0% by mass or more and 7% by mass or less. By containing the curing agent (B) within the above range, the resulting cured product can have superior dielectric properties and a more superior low dielectric loss tangent.

[0060] [Curing Accelerator (C)] The curing accelerator (C) contains one or more of the group consisting of tetraphenylphosphonium-4,4'-sulfonyl diphenol salt, tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate, and 4-hydroxy-2-(triphenylphosphonium)phenol salt. In this embodiment, it may contain two of them.

[0061] From the viewpoint of improving the curing properties of the sealing resin composition, the content of the curing accelerator in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total content of the sealing resin composition. Furthermore, from the viewpoint of obtaining better flowability during the molding of the sealing resin composition, the content of the curing accelerator in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the total content of the sealing resin composition.

[0062] [Coupling Agent (D)] The sealing resin composition of this embodiment may contain a coupling agent (D). Examples of coupling agents (D) include alkylene oxides, mercaptosilanes, phenylaminosilanes, and other aminosilanes. From the viewpoint of improving the adhesion between the sealing material and the metal component, the coupling agent (D) is preferably an alkylene oxide or an aminosilane, and more preferably a secondary aminosilane. From the same viewpoint, the coupling agent (D) is preferably one or more selected from the group consisting of phenylaminopropyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0063] From the viewpoint of obtaining better flowability during the molding of the sealing resin composition, the content of the coupling agent (D) in the sealing resin composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total amount of the sealing resin composition. Furthermore, from the viewpoint of suppressing the thickening of resin viscosity, the content of the coupling agent (D) in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the total amount of the sealing resin composition.

[0064] [Polysilicone oil (E)] The sealing resin composition of this embodiment may contain polysilicone oil (E) as a low-stress agent. This helps to suppress warping of molded articles obtained by sealing electronic components, etc., using the sealing resin composition.

[0065] The polysiloxane oil (E) preferably contains organically modified polysiloxane oils such as epoxy-modified polysiloxane oil, carboxyl-modified polysiloxane oil, alkyl-modified polysiloxane oil, and polyether-modified polysiloxane oil. Among these, from the viewpoint that the polysiloxane oil (E) is micro-dispersed in the resin component, which helps to suppress warping, the presence of polyether-modified polysiloxane oil is particularly preferred.

[0066] The content of polysiloxane (E) is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total amount of the sealing resin composition. Furthermore, the content of polysiloxane (E) is preferably 1% by mass or less, and more preferably 0.5% by mass or less, relative to the total amount of the sealing resin composition. By suppressing the content of polysiloxane (E) within such a range, it is helpful to suppress warping of molded articles obtained by sealing electronic components, etc., using the sealing resin composition.

[0067] In this embodiment, it may contain other low-stress agents besides polysiloxane oil (E). Specific examples include polysiloxane rubber, polysiloxane elastomer, polysiloxane resin, and acrylonitrile-butadiene rubber.

[0068] [Inorganic filler (F)] The sealing resin composition of this embodiment can contain an inorganic filler (F). As the inorganic filler (F), a filler material commonly used in semiconductor sealing resin compositions can be used. Furthermore, the inorganic filler (F) can also be a surface-treated filler material.

[0069] Specific examples of inorganic filler materials (F) include fused silica, crystalline silica, amorphous silica, and other silica; alumina; talc; titanium dioxide; silicon nitride; and aluminum nitride. One of these inorganic filler materials may be used alone, or two or more may be used in combination.

[0070] From the viewpoint of excellent versatility, the inorganic filler material (F) is preferably one containing silicon dioxide. Examples of silicon dioxide shapes include spherical silicon dioxide and broken silicon dioxide.

[0071] From the viewpoint of improving formability and adhesion, the average diameter (D 50) of the inorganic filler material (F) is preferably 5 μm or more, more preferably 10 μm or more, and preferably 80 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less. Here, the particle size distribution of the inorganic filler material (F) can be obtained by measuring the particle size distribution on a volume basis using a commercially available laser diffraction particle size distribution measuring device (e.g., SALD-7000 manufactured by Shimadzu Corporation).

[0072] Furthermore, from the viewpoint of improving formability and adhesion, the maximum particle size of the inorganic filler material (F) is preferably 10 μm or more, more preferably 20 μm or more, and preferably 100 μm or less, more preferably 80 μm or less.

[0073] Furthermore, from the viewpoint of improving formability and adhesion, the specific surface area of ​​the inorganic filler material (F) is preferably 1 m² / g or more, more preferably 3 m² / g or more, and preferably 20 m² / g or less, more preferably 10 m² / g or less.

[0074] From the viewpoint of improving the low hygroscopicity and low thermal expansion of the sealing material formed by using the sealing resin composition, thereby more effectively improving the moisture resistance reliability or reflow resistance of the obtained semiconductor device, the content of inorganic filler (F) in the sealing resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, relative to the total amount of the sealing resin composition. Furthermore, from the viewpoint of more effectively improving the flowability or filling properties of the sealing resin composition during molding, the content of inorganic filler (F) in the sealing resin composition is, for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less, relative to the total amount of the sealing resin composition.

[0075] [Other Components] The sealing resin composition of this embodiment may contain components other than those mentioned above, and may be appropriately blended with one or more of various additives such as flowability improvers, mold release agents, ion trapping agents, flame retardants, colorants, and antioxidants. Furthermore, the sealing resin composition may also contain one or more of, for example, 2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzylamine and 3-amino-5-mercapto-1,2,4-triazole.

[0076] The release agent may contain one or more of the following groups: natural waxes selected from palm wax; synthetic waxes such as octadecanoate wax and oxidized polyethylene wax; higher fatty acids such as zinc stearate and their metal salts; paraffin; and carboxylic acid amides such as sinapic acid amide. From the viewpoint of improving the release properties of the cured form of the sealing resin composition, the content of the release agent in the sealing resin composition relative to the total amount of the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.5% by mass or less.

[0077] Hydrotalcite can be cited as a specific example of an ion scavenger. From the viewpoint of improving the reliability of sealing materials, the content of the ion scavenger in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1.0% by mass or less, more preferably 0.5% by mass or less, relative to the total content of the sealing resin composition.

[0078] Specific examples of flame retardants include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. From the viewpoint of improving the flame retardancy of sealing materials, the content of the flame retardant in the sealing resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 20% by mass or less, more preferably 10% by mass or less, relative to the total content of the sealing resin composition.

[0079] Specific examples of colorants include carbon black and colcothart. From the viewpoint of making the color of the sealing material better, the content of the colorant in the sealing resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less, relative to the total amount of the sealing resin composition.

[0080] Specific examples of antioxidants include hindered phenolic compounds, hindered amine compounds, and thioether compounds.

[0081] <Sealant Composition> The sealant composition of this embodiment is solid at room temperature (25°C), and its shape can be selected according to the molding method of the sealant composition, etc., and examples include ingot; powder, granules, etc.; and flakes.

[0082] Furthermore, regarding the manufacturing method of the sealing resin composition, for example, it can be obtained by mixing the above-mentioned components using a known method, then melting and kneading them using a mixer such as a roller, kneader, or extruder, and finally pulverizing them after cooling. Alternatively, after pulverization, it can be molded to obtain granular or flake-shaped sealing resin compositions. For example, it can also be pressed into ingots to obtain granular sealing resin compositions. Furthermore, flake-shaped sealing resin compositions can also be obtained using, for example, a vacuum extruder. Furthermore, the dispersion or flowability of the obtained sealing resin composition can be appropriately adjusted. Additionally, when the melting point of the active ester resin (B2) is high, it is preferable to pre-melt and uniformly mix the phenolic resin (B1) and the active ester resin (B2).

[0083] The sealing resin composition obtained in this embodiment contains phenolic resin (B1) and reactive ester resin (B2) as hardeners (B), thus enabling the production of a hardened material with low shrinkage, excellent product yield, and superior mechanical strength and dielectric properties. The sealing resin composition of this embodiment can be used for transfer molding, injection molding, or compression molding. Furthermore, by using the sealing resin composition obtained in this embodiment, semiconductor devices with excellent product reliability can be obtained.

[0084] Next, the physical properties of the sealing resin composition or its cured form will be described. In this embodiment, a gel time of 50 seconds or more and 80 seconds or less, and more preferably 55 seconds or more and 70 seconds or less, is preferred. By setting the gel time of the sealing resin composition to the lower limit or above, a package with excellent filling properties can be obtained. On the other hand, by setting the gel time of the sealing resin composition to the upper limit or below, good formability is achieved.

[0085] The cured product obtained from the sealing resin composition of this embodiment has high flexural strength, and the increase in flexural modulus is small compared with conventional cured products. Therefore, it can provide a sealing material with excellent mechanical strength and product reliability. When the sealing resin composition of this embodiment is cured at 175°C for 120 seconds, the cured product has a flexural modulus of 15,000 MPa or more at room temperature (25°C), preferably 16,000 MPa or more, and more preferably 17,000 MPa or more. There is no particular upper limit, and it can be set to 30,000 MPa or less.

[0086] When the sealing resin composition of this embodiment is cured at 175°C for 120 seconds, the flexural strength at room temperature (25°C) is 60 MPa or more, preferably 80 MPa or more, and more preferably 100 MPa or more. There is no particular upper limit, and it can be set to 200 MPa or less.

[0087] In this embodiment, it is preferable to set the upper limit of the molding shrinkage rate of the sealing resin composition to 0.14% or less, more preferably to 0.13% or less, and especially preferably to 0.12% or less. By suppressing the upper limit of the molding shrinkage rate to a lower value, warping of the molded body can be suppressed. On the other hand, it is preferable to set the lower limit of the molding shrinkage rate of the sealing resin composition to -0.5% or more, and more preferably to -0.3% or more. By keeping the molding shrinkage rate within the above range, demolding of the molded body can be made easier. For example, the molding shrinkage rate can be measured using the sealing resin composition, and test pieces produced using a low-pressure injection molding machine (KOHTAKI Corporation's "KTS-15") under conditions of a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds can be measured according to JIS K 6911.

[0088] The dielectric constant of the cured material at a frequency of 5 GHz in this embodiment can be set to 4.0 or less, preferably 3.8 or less, and more preferably 3.6 or less. This allows the cured material to be applied to materials with low dielectric constants.

[0089] The dielectric loss tangent (tanδ) of the hardened material in this embodiment is 0.007 or less, preferably 0.006 or less, and more preferably 0.005 or less when measured at a frequency of 5 GHz. This further improves the dielectric properties of the hardened material.

[0090] In this embodiment, the physical properties of the sealing resin composition and the hardened material can be controlled by appropriately selecting the types or amounts of each component contained in the sealing resin composition and the preparation method of the sealing resin composition.

[0091] <Semiconductor Device> The semiconductor device in this embodiment is a device formed by sealing a semiconductor element with a hardened form of the sealing resin composition described in this embodiment. Specific examples of semiconductor elements include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, solid-state imaging devices, etc. Preferably, the semiconductor element is a so-called element that does not involve the entry or exit of light, excluding light-receiving elements and light-emitting elements (such as light-emitting diodes).

[0092] The substrate of the semiconductor device is, for example, a wiring substrate such as an interposer or a lead frame. Furthermore, the semiconductor element is electrically connected to the substrate via wire bonding or flip-chip bonding.

[0093] Examples of semiconductor devices obtained by sealing semiconductor elements using a sealing resin composition include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Frame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In type eWLB, and Fan-Out type eWLB. The following description will further elaborate on these concepts with reference to the accompanying drawings.

[0094] Figures 1 and 2 are both cross-sectional views showing the configuration of a semiconductor device. However, in this embodiment, the configuration of the semiconductor device is not limited to that shown in Figures 1 and 2. First, the semiconductor device 100 shown in Figure 1 includes a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 formed by sealing the semiconductor element 20. The sealing material 50 is composed of a cured product obtained by curing the sealing resin composition described in this embodiment.

[0095] Furthermore, Figure 1 illustrates a case where the substrate 30 is a circuit board. In this case, as shown in Figure 1, a plurality of solder balls 60 are formed, for example, on the side of the substrate 30 opposite to the side on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on the substrate 30 and electrically connected to the substrate 30 via a wire 40. On the other hand, the semiconductor element 20 can be flip-chip mounted on the substrate 30. Here, the wire 40 is not limited, and examples include Ag wire, Ni wire, Cu wire, Au wire, Al wire, etc. Preferably, the wire 40 is made of an alloy containing Ag, Ni, or Cu or one or more of these.

[0096] The sealing material 50 seals the semiconductor element 20, for example, by covering the side opposite to the side facing the substrate 30. In the example shown in FIG1, the sealing material 50 is formed to cover the aforementioned other side and side surface of the semiconductor element 20. In this embodiment, the sealing material 50 is composed of a cured form of the aforementioned sealing resin composition. Therefore, in the semiconductor device 100, the sealing material 50 has excellent adhesion to the wire 40, thereby improving the reliability of the semiconductor device 100. The sealing material 50 can be formed, for example, by sealing the sealing resin composition using known methods such as transfer molding or compression molding.

[0097] FIG2 is a cross-sectional view showing the configuration of the semiconductor device 100 in this embodiment, and shows an example different from FIG1. ​​The semiconductor device 100 shown in FIG2 uses a lead frame as a substrate 30. In this case, the semiconductor element 20 is mounted on a die pad 32 in the substrate 30, for example, and is electrically connected to the external lead 34 via a wire 40. Furthermore, the sealing material 50 is also made of a cured form of the sealing resin composition in this embodiment, similar to the example shown in FIG1.

[0098] The embodiments of the present invention have been described above, but these are merely examples, and various configurations other than those described above may also be employed. [Examples]

[0099] Hereinafter, the present invention will be described in further detail by way of embodiments, but the present invention is not limited to these embodiments.

[0100] <Examples 1-12, Comparative Examples 1-3 (Preparation of Sealing Resin Composition)> The components listed in Tables 1 and 2 were mixed in the stated proportions to obtain a mixture. The mixture was then mixed at room temperature using a Henschel mixer. Subsequently, the mixture was roller-kneaded at 70-100°C to obtain a compound. The obtained compound was cooled and then pulverized to obtain a sealing resin composition. The components listed in Tables 1 and 2 are described below.

[0101] (Inorganic Filler Materials) • Inorganic Filler Material 1: Silicon dioxide (manufactured by Micron, Inc., product name: TS-6026, average diameter 9μm) • Inorganic Filler Material 2: Micronized silicon dioxide (manufactured by Admatechs, product name: SC-2500-SQ, average diameter 0.6μm) • Inorganic Filler Material 3: Micronized silicon dioxide (manufactured by Admatechs, product name: SC-5500-SQ, average diameter 1.6μm)

[0102] (Flame retardant) .Flame retardant 1: Aluminum hydroxide (manufactured by Nippon Light Metal Company, Ltd., Dp5μm)

[0103] (Coupling Agents) • Silane Coupling Agent 1: N-Phenylaminopropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., CF-4083) • Silane Coupling Agent 2: 3-Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803P) • Silane Coupling Agent 3: 3-Epoxypropoxypropylmethyldimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., AZ-6137)

[0104] (Epoxy Resin) • Epoxy Resin 1: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000L, epoxy equivalent 273g / eq) • Epoxy Resin 2: Multifunctional solid epoxy resin containing a dicyclopentadiene backbone (manufactured by DIC Corporation, EPICLON HP-7200L, epoxy equivalent 246g / eq)

[0105] (Curing Agent) • Phenolic Resin: Phenolic aralkyl type resin containing a biphenyl backbone (manufactured by MEIWA PLASTIC INDUSTRIES, LTD., MEH-7851SS, hydroxyl equivalent 200 g / eq) • Active Ester Resin 1: Active ester resin prepared by the following method (Preparation Method of Active Ester Resin 1) 279.1 g of biphenyl-4,4'-dicarboxylic acid dichloride (moles of chloro groups: 2.0 moles) and 1338 g of toluene were charged into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. The system was then purged with nitrogen under reduced pressure to dissolve the resin. Next, 96.5 g of α-naphthol (0.67 moles) and 219.5 g of dicyclopentadienol resin (moles of phenolic hydroxyl groups: 1.33 moles) were charged into the flask. The system was then purged with nitrogen under reduced pressure to dissolve the resin. Subsequently, while purging with nitrogen and maintaining the system temperature below 60°C, 400g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, stirring continued under these conditions for 1 hour. After the reaction was complete, the mixture was allowed to stand and separated to remove the aqueous layer. Next, water was added to the toluene phase containing the reactants, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand and separated to remove the aqueous layer. This process was repeated until the pH of the aqueous layer reached 7. Subsequently, water was removed by decantation to obtain an active ester resin 1 in a toluene solution containing 65% non-volatile components. The structure of the obtained active ester resin 1 was confirmed, showing that R1 and R3 are hydrogen atoms, Z is a naphthyl group, and l is 0 in the above formula (1-1). Based on the reaction equivalence ratio, the average value k of the repeating units of the active ester resin 1 was in the range of 0.5 to 1.0. Furthermore, the active group equivalent was 247g / eq.

[0106] . Active ester resin 2: Active ester resin prepared by the following method (Preparation method of active ester resin 2): 203.0 g of 1,3-benzenediacarboxylic acid dichloride (moles of chloro groups: 2.0 moles) and 1338 g of toluene were charged into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. The system was purged with nitrogen under reduced pressure to dissolve the resin. Next, 96.5 g of α-naphthol (0.67 moles) and 219.5 g of dicyclopentadienol resin (moles of phenolic hydroxyl groups: 1.33 moles) were charged into the flask. The system was then purged with nitrogen under reduced pressure to dissolve the resin. Subsequently, while purging with nitrogen and maintaining the system temperature below 60°C, 400 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. The mixture was then stirred for another 1.0 hour under these conditions. After the reaction was complete, the mixture was allowed to stand and the aqueous layer was removed. Next, water was added to the toluene phase containing the reactants, and the mixture was stirred for approximately 15 minutes. The mixture was then allowed to stand and separated to remove the aqueous layer. This process was repeated until the pH of the aqueous layer reached 7. Subsequently, water was removed by decantation to obtain an active ester resin 2 in a toluene solution containing 65% non-volatile components. The structure of the obtained active ester resin was confirmed, showing that R1 and R3 are hydrogen atoms, Z is a naphthyl group, and l is 0 in the above formulas (1-3). Based on the reaction equivalence ratio, the average value k of the repeating units of active ester resin 2 is in the range of 0.5 to 1.0. Specifically, the obtained active ester resin 2 has a structure represented by the following chemical formula. Furthermore, the active group equivalent is 209 g / eq.

[0107] (Curing Accelerators) • Curing Accelerator 1: Tetraphenylphosphonium 4,4'-sulfonyldiphenol salt. • Curing Accelerator 2: Tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate. • Curing Accelerator 3: 4-hydroxy-2-(triphenylphosphonium)phenol salt.

[0108] (Ion Scavenger) .Ion Scavenger 1: Magnesium, aluminum, hydroxide, carbonate, hydrate (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H)

[0109] (Wax (Mold Release Agent)) .Wax 1: Oxidized Polyethylene Wax (Manufactured by Clariant (Japan) Co., Ltd., LICOWAX PED191) .Wax 2: Carnauba Wax (Manufactured by TOAKASEI.CO.,LTD., TOWAX-132)

[0110] (Coloring agent) . Carbon black: ERS-2001 (manufactured by TOKAI CARBON CO., LTD.)

[0111] (Low Stress Agent) • Low Stress Agent 1: Carboxyl-terminated butadiene-acrylonitrile copolymer (manufactured by UBE INDUSTRIES, LTD., CTBN1008SP) • Low Stress Agent 2: Epoxy-polyether modified polysiloxane oil (manufactured by Dow Corning Toray Co., Ltd., FZ-3730)

[0112] <Evaluation> Evaluation samples were prepared using the resin compositions obtained in each example or the compositions using the following methods, and the adhesion and reliability of the obtained samples were evaluated using the following methods. [Spiral Flow (SF)] A spiral flow test was performed using the sealing resin compositions of the examples and comparative examples. The test was conducted as follows: The sealing resin composition was injected into a spiral flow measurement mold according to EMMI-1-66 using a low-pressure injection molding machine (KOHTAKI Corporation's "KTS-15") with a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds, and the flow length was measured. The larger the value, the better the flowability.

[0113] [Gel Time (GT)] After melting the sealing resin composition of the Examples and Comparative Examples on a hot plate heated to 175°C, the time (in seconds) until hardening was measured while mixing with a spatula.

[0114] (Glass transition temperature, coefficient of linear expansion (α1 and α2)) Measurements were performed in the following order. (1) The sealing resin composition was injection molded using a transfer molding machine at a mold temperature of 175°C, an injection pressure of 10.0 MPa, and a curing time of 120 seconds to obtain a molded part of 15 mm × 4 mm × 3 mm. (2) The obtained molded part was heated in an oven at 175°C for 4 hours to fully harden it. Then, a test piece (hardened material) for measurement was obtained. (3) Measurements were performed using a thermomechanical analysis apparatus (manufactured by Seiko Instruments Inc., TMA100) at a measurement temperature range of 0°C to 320°C and a heating rate of 5°C / min. Based on the measurement results, the glass transition temperature Tg (°C), the coefficient of linear expansion (α1) at 40–80°C, and the coefficient of linear expansion (α2) at 190–230°C were calculated. The units of α1 and α2 are ppm / °C, and the unit of glass transition temperature is °C.

[0115] [Evaluation of Mechanical Strength (Flexural Strength and Flexural Modulus)] Using a low-pressure injection molding machine (KOHTAKI Corporation's "KTS-30"), a sealing resin composition was injected into a mold at a mold temperature of 175°C, an injection pressure of 10.0 MPa, and a curing time of 120 seconds, and then shaped. A molded article with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm was obtained. The molded article was then post-cured at 175°C for 4 hours. Test pieces were then prepared to evaluate the mechanical strength. The flexural strength (MPa) and flexural modulus (MPa) of the test pieces at 260°C or room temperature (25°C) were then measured according to JIS K 6911.

[0116] (Boiling Water Absorption Rate) For each embodiment and comparative example, the boiling water absorption rate of the cured sealant resin composition was measured as follows. First, a disc-shaped test piece with a diameter of 50 mm and a thickness of 3 mm was formed using a low-pressure injection molding machine (KTS-15 manufactured by KOHTAKI Corporation) at a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds. Next, the obtained test piece was post-cured at 175°C for 4 hours, and the mass of the test piece before boiling treatment and the mass after boiling treatment in pure water for 24 hours were measured. Based on the result of the mass change before and after boiling treatment calculated based on the measurement results, the boiling water absorption rate of the test piece was obtained as a percentage. The units in Table 1 are in mass%.

[0117] (Molding Shrinkage Rate) For each embodiment and comparative example, the molding shrinkage rate (after ASM) of the obtained resin composition was measured. After molding, the molding shrinkage rate (after PMC) was evaluated under heating conditions (PMC) intended for formal curing to produce a dielectric substrate. First, using a low-pressure transfer molding machine (KOHTAKI Corporation's "KTS-15"), the molding shrinkage rate (after ASM) was obtained according to JIS K 6911 for test pieces produced under conditions of mold temperature 175°C, injection pressure 6.9 MPa, and curing time 120 seconds. Then, the obtained test pieces were heat-treated at 175°C for 4 hours, and the molding shrinkage rate (after ASM) was measured according to JIS K 6911.

[0118] (Evaluation of dielectric constant and dielectric loss tangent based on cavity resonator method) First, a test piece was obtained using a resin composition. Specifically, the resin composition prepared in the examples and comparative examples was coated onto a Si substrate and pre-baked at 120°C for 4 minutes to form a resin film with a coating thickness of 12 μm. The film was then subjected to hydrofluoric acid treatment (immersion in a 2% by mass aqueous solution of hydrofluoric acid) in a nitrogen atmosphere at 200°C for 90 minutes. After removing the substrate from the hydrofluoric acid, the hardened film was peeled off from the Si substrate, serving as the test piece. The measuring apparatus used included a network analyzer HP8510C, a synthesis scanner HP83651A, and a tester HP8517B (all manufactured by Agilent Technologies, Ltd.). These apparatuses and a cylindrical cavity resonator (inner diameter φ42 mm, height 30 mm) were assembled. The resonant frequency, 3 dB bandwidth, and transmittance ratio were measured at a frequency of 5 GHz, both with and without the test piece inserted into the resonator. Then, the dielectric properties of the dielectric constant (Dk) and dielectric loss tangent (Df) are determined by analyzing and calculating these measurement results using software. The measurement mode is TE 011 mode.

[0119] [Table 1] Comparative Example 1 Example 1 Example 2 Example 3 Comparative Example 2 Example 4 Example 5 Example 6 Example 7 Comparative Example 3 Inorganic filler materials Inorganic filler material 1 67.00 68.00 68.00 68.00 68.00 68.00 68.00 68.00 68.00 68.00 Inorganic filler material 2 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Inorganic filler material 3 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Flame retardant Flame retardant 1 1.00 Coupling agent Silane coupling agent 1 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Silane coupling agent 2 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Silane coupling agent 3 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Epoxy resin Epoxy Resin 1 6.81 6.67 6.64 6.63 6.62 6.67 6.64 6.63 6.62 Epoxy Resin 2 6.69 hardener Phenolic resin 3.55 2.66 1.87 1.13 2.66 1.87 1.13 2.42 Active ester resin 1 1.06 1.87 2.62 3.76 1.06 1.87 2.62 1.27 3.76 hardening accelerator Hardening accelerator 1 0.04 0.05 0.05 0.05 0.05 0.05 Hardening accelerator 2 0.25 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 Hardening accelerator 3 0.05 0.05 0.05 0.05 Ion scavengers Ion scavenger 1 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Release agent Wax 1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Wax 2 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Colorant carbon black 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Low stress agent Low stress agent 1 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Low stress agent 2 0.40 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Equivalent ratio Active ester resin 1 / epoxy resin - 0.18 0.31 0.44 0.63 0.18 0.31 0.44 0.19 0.63 Equivalent ratio Phenolic resin / epoxy resin 0.70 0.54 0.38 0.23 - 0.54 0.38 0.23 0.44 - Equivalent ratio (Active ester resin 1 + phenolic resin) / epoxy resin 0.70 0.71 0.69 0.67 0.63 0.71 0.69 0.67 0.63 0.63 Spiral Flow cm 110 95 90 89 155 94 91 90 139 154 gel time sec 54 59 60 61 93 58 61 63 59 94 Glass transition temperature deg.C 117 110 125 127 137 109 126 129 131 138 linear expansion coefficient α1 ppm / deg.C 10 9 9 9 8 9 9 9 8 8 linear expansion coefficient α2 ppm / deg.C 40 35 37 38 40 36 36 37 34 39 Bending strength MPa 154 148 140 135 53 149 139 137 98 52 Flexural modulus MPa 20800 23600 24000 24500 26800 23500 24500 24700 26900 26500 Boiling water absorption rate % 0.21 0.19 0.18 0.17 0.14 0.2 0.18 0.18 0.21 0.13 proportion - 2.00 2.00 2.00 2.00 2.01 2.00 2.00 2.00 2.00 2.01 Molding shrinkage % 0.15 0.12 0.08 0.07 0.02 0.10 0.07 0.07 0.10 0.03 Dielectric constant @ 5GHz - 3.7 3.6 3.6 3.6 3.4 3.5 3.6 3.6 3.6 3.4 Dielectric loss tangent @ 5GHz - 0.006 0.005 0.004 0.004 0.002 0.005 0.003 0.003 0.005 0.002

[0120] [Table 2] Example 8 Example 9 Example 10 Example 11 Example 12 Inorganic filler materials Inorganic filler material 1 68.00 68.00 68.00 68.00 68.00 Inorganic filler material 2 10.00 10.00 10.00 10.00 10.00 Inorganic filler material 3 10.00 10.00 10.00 10.00 10.00 Flame retardant Flame retardant 1 Coupling agent Silane coupling agent 1 0.20 0.20 0.20 0.20 0.20 Silane coupling agent 2 0.10 0.10 0.10 0.10 0.10 Silane coupling agent 3 0.10 0.10 0.10 0.10 0.10 Epoxy resin Epoxy Resin 1 6.67 6.64 6.67 6.64 Epoxy Resin 2 6.69 hardener Phenolic resin 2.66 1.87 2.66 1.87 2.42 Active ester resin 2 1.06 1.87 1.06 1.87 1.27 hardening accelerator Hardening accelerator 1 0.05 0.05 0.05 Hardening accelerator 2 0.42 0.42 0.42 0.42 0.42 Hardening accelerator 3 0.05 0.05 Ion scavengers Ion scavenger 1 0.10 0.10 0.10 0.10 0.10 Release agent Wax 1 0.05 0.05 0.05 0.05 0.05 Wax 2 0.10 0.10 0.10 0.10 0.10 Colorant carbon black 0.30 0.30 0.30 0.30 0.30 Low stress agent Low stress agent 1 0.10 0.10 0.10 0.10 0.10 Low stress agent 2 0.10 0.10 0.10 0.10 0.10 total 100.00 100.00 100.00 100.00 100.00 Equivalent ratio Reactive ester resin 2 / epoxy resin 0.21 0.37 0.21 0.37 0.22 Equivalent ratio Phenolic resin / epoxy resin 0.54 0.38 0.54 0.38 0.44 Equivalent ratio (Active ester resin 2 + phenolic resin) / epoxy resin 0.74 0.75 0.74 0.75 0.66 Spiral Flow cm 96 91 95 92 138 gel time sec 58 61 57 62 58 Glass transition temperature deg.C 111 124 108 126 132 linear expansion coefficient α1 ppm / deg.C 9 9 9 9 8 linear expansion coefficient α2 ppm / deg.C 34 37 35 36 34 Bending strength MPa 149 139 147 138 97 Flexural modulus MPa 23000 24000 23000 24000 27000 Boiling water absorption rate % 0.2 0.19 0.21 0.19 0.2 proportion - 2.00 2.00 2.00 2.00 2.00 Molding shrinkage % 0.12 0.09 0.11 0.07 0.11 Dielectric constant @ 5GHz - 3.7 3.6 3.6 3.6 3.6 Dielectric loss tangent @ 5GHz - 0.005 0.004 0.005 0.003 0.005

[0121] As described in Tables 1 and 2, by using both phenolic resin and reactive ester resin as curing agents, and further using a semiconductor sealing resin composition containing a specified curing accelerator, it is envisioned that the shrinkage rate during molding is low and the product yield is excellent. Therefore, it has been confirmed that the cured product obtained from this composition exhibits excellent mechanical strength and dielectric properties. In other words, the excellent balance of these properties of the semiconductor sealing resin composition of the present invention has been confirmed.

[0122] This application claims priority based on Japanese Patent Application No. 2021-117662, filed on July 16, 2021, the entire contents of which are incorporated herein by reference. [Simplified Explanation of the Diagram]

[0011] [Figure 1] is a cross-sectional view showing the configuration of the semiconductor device in the embodiment. [Figure 2] is a cross-sectional view showing the configuration of the semiconductor device in the embodiment.

Claims

1. A resin composition for semiconductor sealing, comprising: (A) an epoxy resin; (B) a curing agent; and (C) a curing accelerator, wherein the curing agent (B) comprises a phenolic resin (B1) and an active ester resin (B2), the phenolic resin (B1) having a biphenyl aralkyl structure, and the active ester resin (B2) having a structure represented by general formula (1), in which A is a substituted or unsubstituted aryl group linked by an aliphatic cyclic hydrocarbon group, Ar' is a substituted or unsubstituted aryl group, k is the average value of repeating units in the range of 0.25 to 3.5, and B is a structure represented by general formula (B) in general formula (1). In general formula (B), Ar is a substituted or unsubstituted aryl group, Y is a single bond, a substituted or unsubstituted linear alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group, an ether bond, a carbonyl group, a carbonyloxy group, a thioether group, or a ternary group, and n is an integer from 0 to 4. The curing accelerator (C) contains one or more of the following groups: tetraphenylphosphonium-4,4'-sulfonylbisphenol salt, tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate, and 4-hydroxy-2-(triphenylphosphonium)phenolate. The equivalent ratio ((B) / (A)) of the curing agent (B) to the epoxy resin (A) is 0.60 to 0.

90. The equivalent ratio of phenolic resin (B1) to epoxy resin (A) ((B1) / (A)) is 0.10 to 0.55, and the equivalent ratio of reactive ester resin (B2) to epoxy resin (A) ((B2) / (A)) is 0.10 to 0.

60.

2. The semiconductor sealing resin composition as claimed in claim 1, wherein, The aforementioned structure represented by general formula (B) is selected from at least one of general formulas (B-1) to (B-6). In general formulas (B-1) to (B-6), R1 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; R2 is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; X is any one of a straight-chain extended alkyl group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a thioether group, or a ternary group; n is an integer from 0 to 4; and p is an integer from 1 to 4.

3. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, In the aforementioned general formula (1), A has a structure represented by general formula (A), in which R3 is independently any one of hydrogen atom, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenyl, aralkyl, l is 0 or 1, and m is an integer greater than or equal to 1.

4. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, The ratio of the content (parts by weight) of phenolic resin (B1) to the content (parts by weight) of active ester resin (B2) is 25:75 to 75:

25.

5. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, The curing accelerator (C) is a combination of (C1) tetraphenylphosphonium-4,4'-sulfadiphenol salt and tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate, or a combination of (C2) tetraphenylphosphonium bis(naphthalene-2,3-dioxy)phenyl silicate and 4-hydroxy-2-(triphenylphosphonium)phenol salt.

6. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, The resin composition for semiconductor sealing contains a curing accelerator (C) in an amount of 0.01% by mass or more and 2.0% by mass or less, relative to the total composition of the aforementioned semiconductor sealing resin.

7. The semiconductor sealing resin composition of claim 1 or 2 further contains a coupling agent (D).

8. The semiconductor sealing resin composition as claimed in claim 7, wherein, The coupling agent (D) is a secondary aminosilane coupling agent.

9. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, Epoxy resin (A) has a biphenyl aryl alkyl structure.

10. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, The epoxy resin (A) contains at least one type selected from biphenyl aryl resins and dicyclopentadiene resins.

11. The semiconductor sealing resin composition of claim 1 or 2 further contains polysiloxane oil (E).

12. The semiconductor sealing resin composition of claim 1 or 2 further contains an inorganic filler (F).

13. The semiconductor sealing resin composition as claimed in claim 12, wherein, The inorganic filler (F) is selected from at least one of silicon dioxide, alumina, talc, titanium dioxide, silicon nitride, and aluminum nitride.

14. The semiconductor sealing resin composition as claimed in claim 1 or 2, wherein, The gel time of the resin composition for semiconductor sealing is more than 50 seconds and less than 80 seconds.

15. A semiconductor device comprising: a semiconductor element; and a sealing material, which is composed of a hardened form of a semiconductor sealing resin composition of any one of claims 1 to 14, and which seals the aforementioned semiconductor element.

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