Epoxy resin composition, cured product, and semiconductor device

Abstract

Provided is an epoxy resin composition that is unlikely to undergo delamination. Also provided are a cured product of the epoxy resin composition, a semiconductor device provided with the cured product, and a method for producing the semiconductor device.　This epoxy resin composition contains an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C). The epoxy resin (A) contains an aminophenol-type epoxy resin (A1) and a low-shrinkage epoxy resin (A2).

Description

Epoxy resin composition, cured product, and semiconductor device

[0001] The present invention relates to an epoxy resin composition, a cured product, a semiconductor device, and a method for producing a semiconductor device.

[0002] Many semiconductor elements, such as integrated circuits, that make up semiconductor devices are used in a state where they are encapsulated with an encapsulant. There are several methods for encapsulating semiconductor elements, one of which is known as compression molding. Compression molding involves placing a liquid or granular resin encapsulant into a mold, heating and melting it as needed, and compressing and molding it. This method is suitable for producing relatively large molded products. In recent years, compression molding has been increasingly used to encapsulate semiconductor elements. This is due in part to the widespread use of wafer-level chip-size packaging technology. This technology involves compression molding using an encapsulant (compression molding material) at the wafer stage, hardening it to encapsulate multiple semiconductor elements at once, and then separating them into individual pieces.

[0003] Conventional curable resin compositions used for encapsulating semiconductor elements by compression molding have generally been solid (e.g., granular) compositions. However, in recent years, with the development of new compression molding techniques, liquid curable resin compositions have increasingly been used. Such liquid curable resin compositions are called liquid compression molding (LCM) materials. Liquid epoxy resin compositions are used as LCM materials from the viewpoint of balancing various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness.

[0004] Compared to methods in which semiconductor elements are diced and then sealed, wafer-level chip size packaging offers higher productivity, but the problem is that the wafer is prone to warping after molding (sealing).Warping of the wafer can have adverse effects, such as insufficient wafer fixation, in subsequent processes such as transportation, grinding, and dicing, which can result in reduced reliability of the semiconductor device.

[0005] To solve these problems, various encapsulating materials have been investigated. For example, Patent Document 1 discloses a liquid epoxy resin composition for encapsulation containing a liquid bisphenol-type epoxy resin, silicone rubber microparticles, a silicone-modified epoxy resin, an aromatic amine curing agent, an inorganic filler, and an organic solvent. Patent Document 2 also discloses a liquid epoxy resin composition for encapsulation containing a liquid epoxy resin, an aromatic amine curing agent, microparticles of a core-shell silicone polymer having a solid silicone polymer core and an organic polymer shell, an inorganic filler, and an organic solvent. However, even when these epoxy resin compositions are used as LCM materials, warpage of the wafer after molding (encapsulation) sometimes occurs.

[0006] JP 2007-023272 A JP 2008-150555 A

[0007] In LCM materials, one method for reducing wafer warpage after molding (encapsulation) is to use an aminophenol-type epoxy resin as the epoxy resin. However, when a composition containing an aminophenol-type epoxy resin is used as an LCM material, there is a problem of delamination being easily generated. Here, delamination refers to the occurrence of "peeling" or "lifting" of the cured LCM material in part or all of the vicinity of the interface (i.e., the boundary) between the wafer and the chip when the LCM material is supplied to the chip mounted on the wafer surface and then molded. Referring to Figure 3, in (B) and (C), "peeling" or "lifting" of the cured material occurs in part or all of the chip side surfaces on the wafer surface after molding, and this is defined as delamination in this specification.

[0008] Since the occurrence of delamination impairs the reliability of semiconductor devices, there is a need to suppress the occurrence of delamination. Therefore, an object of the present invention is to provide an epoxy resin composition that is less susceptible to delamination. It is also an object of the present invention to provide a cured product of the epoxy resin composition, a semiconductor device including the cured product, and a method for manufacturing the semiconductor device.

[0009] As a result of extensive research to achieve the above object, the inventors discovered that delamination occurs close to the gel time and that cure shrinkage of the resin is the cause of delamination. Taking this into consideration, they found that the above problem can be solved by blending specific components into the composition. The present invention was completed based on these findings.

[0010] That is, the present invention provides an epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), wherein the epoxy resin (A) comprises an aminophenol-type epoxy resin (A1) and a low-shrinkage epoxy resin (A2).

[0011] The content of the aminophenol type epoxy resin (A1) relative to the epoxy resin (A) is preferably 28 to 60 mass %.

[0012] The content of the low-shrinkage epoxy resin (A2) relative to the aminophenol-type epoxy resin (A1) is preferably 5 to 150% by mass.

[0013] The epoxy resin composition preferably further contains a curing agent (D).

[0014] The epoxy resin composition preferably contains, as the low-shrinkage epoxy resin (A2), at least one selected from the group consisting of oxazolidone ring-containing epoxy resins, naphthalene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and trisphenolmethane-type epoxy resins.

[0015] The epoxy resin composition preferably contains an oxazolidone ring-containing epoxy resin as the low-shrinkage epoxy resin (A2).

[0016] The epoxy resin composition preferably contains a naphthalene-type epoxy resin as the low-shrinkage epoxy resin (A2).

[0017] The epoxy resin composition preferably further contains an aliphatic epoxy resin (A3) as the epoxy resin (A).

[0018] The curing accelerator (B) preferably contains an imidazole-based curing accelerator.

[0019] The curing agent (D) preferably contains an acid anhydride-based curing agent and / or a phenol-based curing agent.

[0020] The content of the epoxy resin (A) relative to the epoxy resin composition (100% by mass) is preferably 9% by mass or more.

[0021] The content of the curing accelerator (B) relative to the epoxy resin (A) (100% by mass) is preferably 0.5 to 15% by mass.

[0022] The epoxy resin composition is preferably a liquid compression molding material.

[0023] The present invention also provides a cured product of the above epoxy resin composition.

[0024] The present invention also provides a semiconductor device comprising the above-mentioned cured product.

[0025] The present invention also provides a semiconductor device comprising: a support; a semiconductor element mounted on the support; and the cured product that encapsulates the semiconductor element.

[0026] The present invention also provides a method for manufacturing a semiconductor device, which includes the steps of: supplying the epoxy resin composition onto a laminate including a support and a semiconductor element mounted on the support; filling a gap between the support and the semiconductor element with the epoxy resin composition to form a molded body; and curing the molded body to encapsulate the semiconductor element, thereby obtaining an encapsulated body.

[0027] The method for manufacturing a semiconductor device preferably further includes the step of polishing the sealing body.

[0028] The epoxy resin composition of the present invention is less susceptible to delamination, and therefore semiconductor devices comprising a cured product of the epoxy resin composition exhibit high reliability.

[0029] 1A to 1C are cross-sectional SEM images of the side surfaces of chips in an example and a comparative example;

[0030] <Epoxy Resin Composition> The epoxy resin composition of the present invention comprises an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), wherein the epoxy resin (A) comprises an aminophenol-type epoxy resin (A1) and a low-shrinkage epoxy resin (A2). The epoxy resin composition may further comprise a curing agent (D).

[0031] Epoxy Resin (A) The epoxy resin composition contains the epoxy resin (A), which allows it to form a cured product with high electrical insulation. The number of epoxy groups in the epoxy resin (A) is not particularly limited as long as it is one or more, but it is preferably two or more (i.e., a polyfunctional epoxy resin). The epoxy resin (A) can be used alone or in combination of two or more.

[0032] The epoxy resin (A) may be liquid or solid at room temperature (25° C.), but is preferably liquid from the viewpoint of the viscosity of the epoxy resin composition. A solid epoxy resin can also be preferably used when it is used in combination with a liquid epoxy resin to form a liquid mixture.

[0033] Examples of the epoxy resin (A) include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol AF-type epoxy resins; bixylenol-type epoxy resins, cyclohexane-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenolmethane-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, and anthracene-type epoxy resins. resins, oxazolidone ring-containing epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylmethane-type epoxy resins, aminophenol-type epoxy resins, and silicone-modified epoxy resins.

[0034] The epoxy resin composition contains an aminophenol-type epoxy resin (A1) and a low-shrinkage epoxy resin (A2) as the epoxy resin (A). The low-shrinkage epoxy resin (A2) refers to an epoxy resin having a smaller cure shrinkage rate than the aminophenol-type epoxy resin. Examples of the low-shrinkage epoxy resin (A2) include oxazolidone ring-containing epoxy resins, naphthalene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and trisphenolmethane-type epoxy resins. These epoxy resins can be said to have a smaller cure shrinkage rate than the aminophenol-type epoxy resins.

[0035] The aminophenol-type epoxy resin (A1) is used to suppress warpage after molding. The aminophenol-type epoxy resin (A1) is also used to improve the glass transition temperature (and thus improve heat resistance), provide low viscosity, and reduce the amount of chlorine. On the other hand, the aminophenol-type epoxy resin (A1) is an epoxy resin with a relatively large cure shrinkage, and therefore epoxy resin compositions containing it tend to be prone to delamination. As described above, delamination is believed to be caused by the cure shrinkage of the epoxy resin. The present invention aims to reduce the cure shrinkage of the epoxy resin as a whole during curing by using the aminophenol-type epoxy resin (A1) in combination with the low-shrinkage epoxy resin (A2), thereby suppressing delamination. To further suppress delamination, the low-shrinkage epoxy resin (A2) preferably contains an oxazolidone ring-containing epoxy resin and / or a naphthalene-type epoxy resin, and more preferably contains an oxazolidone ring-containing epoxy resin.

[0036] In order to suppress the occurrence of warpage after molding, the epoxy resin composition preferably further contains an aliphatic epoxy resin (A3) as the epoxy resin (A). The aliphatic epoxy resin (A3) is an epoxy resin with a relatively large cure shrinkage rate, similar to aminophenol-type epoxy resins.

[0037] Specific examples of liquid epoxy resins include "YDF-8170" and "YDF870GS" (both bisphenol F type epoxy resins), "YDF-8125" (bisphenol A type epoxy resin), "ZX-1658" and "ZX-1658GS" (all liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "HP-4032", "HP-4032D", and "HP-4032SS" (all naphthalene type epoxy resins) manufactured by DIC Corporation; and "jER828US" and "jER828EL" (both bisphenol A type epoxy resins) and "jER828" manufactured by Mitsubishi Chemical Corporation. 06, "jER807" (all bisphenol F type epoxy resins), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD" (all aminophenol type epoxy resins), "YX7400N" (aliphatic epoxy resin / polytetramethylene glycol diglycidyl ether); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) and "EX-171" (lauryl alcohol (EO)) manufactured by Nagase ChemteX Corporation. １５ glycidyl ether); ADEKA Corporation's "ADEKA RESIN EP4005" (bisphenol A type epoxy resin containing a polypropylene glycol structure), "EP-3950L" (aminophenol type epoxy resin), and "EP3980S" (glycidylamine type epoxy resin); Asahi Kasei Corporation's "AER9000" (PO-modified bisphenol type epoxy resin), "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins); The Dow Chemical Company's "DER852" and "DER858" (all oxazolidone ring-containing epoxy resins); Nippon Kayaku Co., Ltd.'s "FAE-2500" and "EPPN-501HY" (all trisphenolmethane type epoxy resins); and Daicel Corporation's "Celloxide 2021P" (alicyclic epoxy resin).

[0038] Specific examples of solid epoxy resins include "HP-4032H" (naphthalene type epoxy resin), "HP-4700", and "HP-4710" (all naphthalene type tetrafunctional epoxy resins), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", and "HP-7200HHH" (all dicyclopentadiene type epoxy resins), all manufactured by DIC Corporation. ene-type epoxy resins), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", and "HP6000" (all naphthylene ether-type epoxy resins); "EPPN-502H" (trisphenolmethane-type epoxy resin), "NC-7000-L" (naphthol novolac-type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", and "NC-310" manufactured by Nippon Kayaku Co., Ltd. 0" (all biphenyl-type epoxy resins); "ESN475V" (naphthol-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H" and "YL6121" (both biphenyl-type epoxy resins), "YX4000HK" (bixylenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; and "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "jER157S70" (bisphenol novolac-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

[0039] The content of the epoxy resin (A) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 9% by mass or more, and particularly preferably 12% by mass or more. It is also preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less. That is, the content of the epoxy resin (A) relative to the epoxy resin composition (100% by mass) is preferably 3 to 60% by mass, more preferably 6 to 50% by mass, even more preferably 9 to 40% by mass, and particularly preferably 12 to 35% by mass. Having the epoxy resin (A) content within the above range tends to result in a cured product with high electrical insulation.

[0040] The content of the aminophenol-type epoxy resin (A1) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is not particularly limited, but is preferably 20% by mass or more, more preferably 24% by mass or more, even more preferably 28% by mass or more, and particularly preferably 30% by mass or more. It is also preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. That is, the content of the aminophenol-type epoxy resin (A1) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is preferably 20 to 80% by mass, more preferably 24 to 70% by mass, even more preferably 28 to 60% by mass, and particularly preferably 30 to 55% by mass. By having the aminophenol-type epoxy resin (A1) content within the above range, the glass transition temperature of the cured product tends to be improved. Furthermore, warpage after molding is reduced, and delamination tends to be less likely to occur. In particular, when the content of the aminophenol-type epoxy resin (A1) is 60 mass% or less, delamination tends to occur less easily.

[0041] The content of the low-shrinkage epoxy resin (A2) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is not particularly limited, but is preferably, for example, 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. It is also preferably, for example, 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. That is, the content of the low-shrinkage epoxy resin (A2) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is, for example, preferably 3 to 80% by mass, more preferably 5 to 70% by mass, even more preferably 8 to 60% by mass, and particularly preferably 8 to 55% by mass. Having the content of the low-shrinkage epoxy resin (A2) within the above range reduces warpage after molding and tends to make delamination less likely to occur.

[0042] The content of the aliphatic epoxy resin (A3) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is not particularly limited, but is preferably, for example, 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. It is also preferably, for example, 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. That is, the content of the aliphatic epoxy resin (A3) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is, for example, preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass. Having the aliphatic epoxy resin (A3) content within the above range reduces warpage after molding and tends to make delamination less likely to occur.

[0043] The content of the low-shrinkage epoxy resin (A2) relative to the aminophenol-type epoxy resin (A1) (100% by mass) in the epoxy resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more. It is also preferably 200% by mass or less, more preferably 150% by mass or less, even more preferably 140% by mass or less, and particularly preferably 130% by mass or less. That is, the content of the low-shrinkage epoxy resin (A2) relative to the aminophenol-type epoxy resin (A1) (100% by mass) in the epoxy resin composition is, for example, preferably 1 to 200% by mass, more preferably 3 to 150% by mass, even more preferably 5 to 140% by mass, even more preferably 10 to 130% by mass, and particularly preferably 15 to 130% by mass. The content of the low-shrinkage epoxy resin (A2) within the above range tends to improve the glass transition temperature of the cured product. Furthermore, warpage after molding is reduced and delamination tends to be less likely to occur.

[0044] In the epoxy resin composition, the content of the alicyclic epoxy resin relative to the epoxy resin (A) (100% by mass) is preferably 36% by mass or less, more preferably 18% by mass or less, even more preferably 9% by mass or less, even more preferably 3% by mass or less, and particularly preferably 0% by mass (i.e., the epoxy resin composition does not contain any alicyclic epoxy resin). When the content of the alicyclic epoxy resin is within the above range, the occurrence of delamination tends to be suppressed. In particular, when the content is 9% by mass or less, this tendency is more pronounced.

[0045] Curing accelerator (B) The curing accelerator (B) has the property of accelerating the curing of the epoxy resin. The curing accelerator is not particularly limited, but examples thereof include imidazole-based curing accelerators, tertiary amine-based curing accelerators, and phosphorus-based curing accelerators. Among these, imidazole-based curing accelerators are preferred from the viewpoint of reliability. The curing accelerator (B) can be used alone or in combination of two or more.

[0046] Examples of the imidazole curing accelerator include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. Commercially available products include 2-ethyl-4-methylimidazole (product name "2E4MZ"), 2-phenyl-4-methylimidazole (product name "2P4MZ"), 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name "2P4MHZ-PW"), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product name "2MZA-PW"), "2MZ-OK", "2MA-OK", and "2PHZ", all manufactured by Shikoku Chemical Industry Co., Ltd. In addition, encapsulated imidazole, also known as microencapsulated imidazole or epoxy adduct imidazole, may also be used. Commercially available products include "HX3941HP", "HXA3942HP", "HXA3922HP", "HXA3792", "HX3748", "HX3721", "HX3722", "HX3088", "HX3741", "HX3742", and "HX3613" (all manufactured by Asahi Kasei Chemicals Corporation), "PN-23J", "PN-40J", and "PN-50" (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and "FXR-1121" (manufactured by Fuji Chemical Industry Co., Ltd.).

[0047] Examples of tertiary amine curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N'-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene, 1,5-diazabicyclo[4.3.0]nonene, and salts thereof. Examples of the salts include the formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, and phenol novolac resin salt of 1,8-diazabicyclo[5.4.0]undecene, and the formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, and phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]nonene.

[0048] Examples of phosphorus-based curing accelerators include phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane, and 1,2-bis-(diphenylphosphino)ethane.

[0049] The content of the curing accelerator (B) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. It is also preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. That is, the content of the curing accelerator (B) relative to the epoxy resin composition (100% by mass) is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, even more preferably 0.1 to 3% by mass, even more preferably 0.2 to 2% by mass, and particularly preferably 0.5 to 2% by mass. Having the curing accelerator (B) content within the above range tends to improve curability and result in better molding. Furthermore, the cured product tends to be less susceptible to deterioration over time.

[0050] The content of the curing accelerator (B) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and particularly preferably 2.5% by mass or more. The content is preferably 15% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less. That is, the content of the curing accelerator (B) relative to the epoxy resin (A) (100% by mass) in the epoxy resin composition is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass, even more preferably 1.5 to 10% by mass, even more preferably 2 to 7% by mass, and particularly preferably 2.5 to 7% by mass. Having the curing accelerator (B) content within the above range tends to improve curability and result in good molding properties. Furthermore, the cured product tends to be less susceptible to deterioration over time.

[0051] Inorganic Filler (C) The inorganic filler (C) is not particularly limited, but is preferably (1) one having the property of suppressing volumetric shrinkage (cure shrinkage) resulting from the curing reaction of the epoxy resin composition, (2) one having the property of suppressing volumetric change due to heating of the cured product (thermal shrinkage), i.e., one having the effect of lowering the linear expansion coefficient when added, or (3) one having both of these properties.

[0052] Examples of inorganic fillers (C) include silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, lime sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and inorganic particles having their surfaces treated. Among these, silica is preferred from the viewpoint of increasing the loading amount. Furthermore, alumina is preferred from the viewpoint of high thermal conductivity. The inorganic filler (C) can be used alone or in combination of two or more.

[0053] In order to maintain the viscosity of the epoxy resin composition within an appropriate range, the inorganic filler (C) is preferably surface-treated with a coupling agent having a functional group such as an epoxy group, a (meth)acryloyl group, or an amino group (particularly a phenylamino group). Examples of the coupling agent include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. For the surface treatment of the inorganic filler (C), one of the above coupling agents can be used alone, or two or more can be used in combination.

[0054] Commercially available products of the inorganic filler (C) include "YA050C-SM1" (silicon dioxide surface-treated with 3-methacryloxypropyltrimethoxysilane, average particle size 0.05 μm) and "SE1050-SMO" (silicon dioxide surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.3 μm) manufactured by Admatechs Co., Ltd.

[0055] The shape of the inorganic filler (C) is not particularly limited, and examples thereof include spherical (e.g., spherical, nearly spherical), polyhedral, rod-like (e.g., cylindrical, prismatic), plate-like, flaky, and irregular shapes. Among these, spherical shapes are preferred from the viewpoint of achieving a high loading amount.

[0056] The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 1 nm to 15 μm, more preferably 5 nm to 10 μm, even more preferably 10 nm to 5 μm, even more preferably 20 nm to 1 μm, and particularly preferably 30 nm to 0.5 μm. When the average particle size of the inorganic filler (C) is within the above range, the particle size is not too large, and therefore the epoxy resin composition tends to have high filling properties even in narrow gaps. Two or more inorganic fillers with different average particle sizes may be used in combination to adjust the viscosity of the epoxy resin composition. In this specification, the method for measuring the average particle size of the inorganic filler (C) is not particularly limited, but can be measured, for example, using a laser diffraction / scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0057] The epoxy resin composition may contain two or more inorganic fillers with different average particle sizes. Specifically, the inorganic filler (C) preferably contains an inorganic filler (C1) having an average particle size of 100 nm to 10 μm and an inorganic filler (C2) having an average particle size of 1 nm or more but less than 100 nm. The average particle size of the inorganic filler (C1) is not particularly limited as long as it is 100 nm to 10 μm, but is preferably, for example, 200 nm or more, and more preferably 250 nm or more. It is also preferably, for example, 5 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less. The average particle size of the inorganic filler (C2) is not particularly limited as long as it is 1 nm or more but less than 100 nm, but is, for example, preferably 5 nm or more, and more preferably 10 nm or more. It is also, for example, preferably 80 nm or less, and more preferably 60 nm or less.

[0058] When the epoxy resin composition contains silica as the inorganic filler (C), it is preferable to use a first silica having an average particle size of 10 nm or more but less than 100 nm in combination with a second silica having an average particle size of 0.1 to 5.0 μm. When the epoxy resin composition contains alumina as the inorganic filler (C), it is preferable that the average particle size thereof be 0.1 to 5.0 μm.

[0059] The content of the inorganic filler (C) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 72% by mass or more, even more preferably 74% by mass or more, and particularly preferably 78% by mass or more. It is also preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 88% by mass or less, even more preferably 86% by mass or less, even more preferably 82% by mass or less, and particularly preferably 81% by mass or less. That is, the content of the inorganic filler (C) relative to the epoxy resin composition (100% by mass) is, for example, preferably 30 to 95% by mass, more preferably 50 to 90% by mass, even more preferably 60 to 88% by mass, even more preferably 70 to 86% by mass, even more preferably 72 to 82% by mass, even more preferably 74 to 81% by mass, and particularly preferably 78 to 81% by mass. When the content of the inorganic filler (C) is within the above range, the gap filling property and workability of the epoxy resin composition are improved, warpage after molding is reduced, and further, delamination tends to be less likely to occur.

[0060] Curing agent (D) The curing agent (D) is not particularly limited as long as it initiates, progresses, or accelerates the polymerization of the epoxy resin, but for example, it preferably contains at least one selected from the group consisting of an amine-based curing agent, an acid anhydride-based curing agent, and a phenol-based curing agent, more preferably contains an acid anhydride-based curing agent and / or a phenol-based curing agent, and even more preferably contains a phenol-based curing agent. The curing agent (D) can be used alone or in combination of two or more types.

[0061] Examples of the amine-based curing agent include aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. Examples of the acid anhydride-based curing agent include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadic anhydride. Examples of the phenol-based curing agent include phenol novolac resin, cresol novolac resin, naphthol-modified phenolic resin, dicyclopentadiene-modified phenolic resin, and p-xylene-modified phenolic resin.

[0062] The content of the curing agent (D) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. It is also preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. That is, the content of the curing agent (D) relative to the epoxy resin composition (100% by mass) is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, even more preferably 0.1 to 3% by mass, even more preferably 0.2 to 2% by mass, and particularly preferably 0.5 to 2% by mass. Having the curing agent (D) content within the above range tends to improve curability and result in better molding. Furthermore, the cured product tends to be less susceptible to deterioration over time.

[0063] The content of the curing agent (D) relative to the epoxy resin composition (100% by mass) excluding the inorganic filler (C) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more. It is also preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. That is, the content of the curing agent (D) relative to the epoxy resin composition (100% by mass) excluding the inorganic filler (C) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 2 to 15% by mass. When the content of the curing agent (D) is within the above range, curability is improved and molding performance tends to be improved. Furthermore, the cured product tends to be less susceptible to deterioration over time.

[0064] Other Components (E) The epoxy resin composition may contain components other than the epoxy resin (A), the curing accelerator (B), the inorganic filler (C), and the curing agent (D) (hereinafter referred to as "other components (E)"). Examples of other components (E) include curable compounds other than the epoxy resin (A), thermoplastic resins such as polyethylene resins, polyester resins, polyurethane resins, and polyamide resins, coupling agents, elastomers, surfactants, ion trapping agents, leveling agents, antioxidants, antifoaming agents, flame retardants, colorants such as carbon black, reactive diluents, and solvents. The other components (E) may be used alone or in combination of two or more.

[0065] Examples of the coupling agent include various coupling agents such as vinyl-based, glycidoxy-based, (meth)acrylic-based, amino-based, mercapto-based, and imidazole-based silane coupling agents; alkoxide-based, chelate-based, and acylate-based titanium coupling agents; and long-chain spacer coupling agents such as glycidoxyoctyltrimethoxysilane and methacrylooctyltrimethoxysilane. Examples of the silane coupling agent include 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

[0066] Examples of the elastomer include butadiene-based elastomers, silicone-based elastomers, acrylic copolymers, and styrene-butadiene-based elastomers. The elastomer may be a core-shell rubber particle. That is, it may be a core-shell rubber type elastomer. The core-shell rubber particle refers to a rubber particle composed of a core and one or more shell layers covering the core.

[0067] The content of the other component (E) relative to the epoxy resin composition (100% by mass) is not particularly limited as long as it does not impair the effects of the present invention, but is, for example, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. Also, for example, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more.

[0068] The content of the solvent relative to the epoxy resin composition (100% by mass) is, for example, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.1% by mass or less. Alternatively, it is, for example, 0.01% by mass or more, or 0.1% by mass or more. The epoxy resin composition may contain a solvent, but it is desirable that the composition be substantially free of solvent, since unintended voids may be generated due to evaporation of the solvent during curing.

[0069] (Physical Properties and Production Method of Epoxy Resin Composition) The viscosity of the epoxy resin composition at 25°C is not particularly limited, but is, for example, preferably 1 to 1,000 Pa·s, more preferably 10 to 800 Pa·s, even more preferably 50 to 500 Pa·s, and particularly preferably 100 to 300 Pa·s. Having a viscosity within the above range improves the gap-filling properties and workability of the epoxy resin composition, and also tends to reduce warpage of the wafer after molding. The viscosity can be measured using a Brookfield viscometer at a liquid temperature of 25°C, as the viscosity when rotated at 10 rpm for 1 minute.

[0070] The epoxy resin composition can be prepared by a known, conventional method. For example, the epoxy resin (A), curing accelerator (B), inorganic filler (C), and optionally at least one component selected from the group consisting of curing agent (D) and other components (E) can be simultaneously or separately introduced into an appropriate mixer and stirred and mixed while melting by heating as needed. When the epoxy resin (A) is solid, it is preferably liquefied or fluidized by heating before mixing. If it is difficult to uniformly disperse the inorganic filler (C) in the epoxy resin composition, the epoxy resin (A) and inorganic filler (C) can be heated and mixed to uniformly disperse the inorganic filler (C) in the epoxy resin (A), followed by cooling as needed, and then mixing with components such as the curing agent (D). This can also be used to prepare the epoxy resin composition.

[0071] The mixer is not particularly limited, and examples thereof include a roll mill equipped with a stirrer and a heater, a Raikai mixer, a Henschel mixer, a tumbler, a planetary mixer, etc. The mixing ratio of each component is appropriately set depending on the content of each component in the epoxy resin composition.

[0072] The epoxy resin composition can be preferably used as a material for encapsulating materials mounted on a support, such as a semiconductor element, wiring, and solder (solder bumps) in a semiconductor device (an epoxy resin composition for semiconductor encapsulation). By using the epoxy resin composition as an epoxy resin composition for semiconductor encapsulation, a highly reliable encapsulated body can be produced. The epoxy resin composition can also be preferably used as a material for encapsulating a semiconductor element or the like mounted on a support in a flip-chip semiconductor device (an epoxy resin composition for flip-chip semiconductor encapsulation). Specifically, by filling the gap between the semiconductor element or the like and the support and curing the epoxy resin composition, the bumps present in the gap can be encapsulated while the semiconductor element and the support are fixed together as an encapsulated body, thereby improving thermal cycle resistance.

[0073] The epoxy resin composition is used, for example, as an underfill such as a capillary underfill, a liquid mold underfill, a secondary underfill, or a pre-applied underfill; a grab-top material; or a liquid compression molding material. Among these, when the epoxy resin composition is used as a liquid compression molding material, it is preferred because it fully exhibits the property of suppressing the occurrence of delamination. Furthermore, the epoxy resin composition is not limited to the use as the epoxy resin composition for semiconductor encapsulation described above, and can be used, for example, as an adhesive for fixing, joining, or protecting components that constitute electronic components.

[0074] <Cured Product> A cured product is formed by curing the epoxy resin composition. The curing method is not particularly limited, but can be carried out, for example, by subjecting the epoxy resin composition to a heat treatment. The temperature for the heat treatment is not particularly limited, but is preferably, for example, 60 to 200°C, and more preferably 80 to 180°C. The time for the heat treatment is not particularly limited, but is, for example, preferably 0.1 to 5 hours, and more preferably 0.5 to 3 hours.

[0075] The glass transition temperature (Tg) of the cured product obtained by heat-curing the epoxy resin composition at 165°C for 120 minutes is not particularly limited, but is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, and particularly preferably 150°C or higher. The glass transition temperature (Tg) is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. The storage modulus (E') and loss modulus (E'') of the cured product of the epoxy resin composition were measured using a dynamic viscoelasticity analyzer, and the glass transition temperature (Tg) was calculated as the peak value of tan δ, which is the ratio of these values. The measurement was performed in accordance with Japanese Industrial Standard JIS C6481.

[0076] <Semiconductor device and manufacturing method thereof> The semiconductor device of the present invention comprises a support, a semiconductor element mounted on the support, and a cured product of the epoxy resin composition that encapsulates the semiconductor element. The semiconductor device is preferably a flip-chip type semiconductor device. A flip-chip type semiconductor device has a structure in which an electrode portion on the support is connected to the semiconductor element via a bump electrode. In addition, in the semiconductor device, the gap between the semiconductor element and the support is encapsulated with a cured product (encapsulant) of the epoxy resin composition.

[0077] The method for manufacturing a semiconductor device of the present invention is characterized by comprising: a step of supplying the epoxy resin composition onto a laminate including a support and a semiconductor element mounted on the support (hereinafter referred to as the "composition supplying step"); and a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to encapsulate the semiconductor element, and obtaining an encapsulated body (hereinafter referred to as the "molding and encapsulating step").

[0078] The method for manufacturing a semiconductor device of the present invention may further include a step of polishing the sealing body (hereinafter referred to as a "grinding step"). Also, it may include at least one step selected from the group consisting of a stack preparation step and a singulation step, which will be described later.

[0079] (Laminate preparation process) The laminate preparation process is a process of mounting a semiconductor element on a support to prepare a laminate including a support and a semiconductor element mounted on the support. In the laminate, the support and the semiconductor element may be connected via solder, or may be connected using an adhesive film or adhesive sheet such as a die attach film (DAF). The support is not particularly limited, but examples thereof include silicon wafers, silicon carbide wafers, sapphire wafers, compound semiconductor wafers (gallium phosphide, gallium arsenide, indium phosphide, gallium nitride), glass epoxy substrates, organic substrates (FR4 substrates), etc. The shape of the support in a planar view is not particularly limited, but is, for example, circular or rectangular.

[0080] (Composition Supplying Step) The composition supplying step is a step of supplying the epoxy resin composition onto a laminate including a support and a semiconductor element mounted on the support.

[0081] This step may include a step of attaching a mold to the laminate, which is used to form a molded article in the molding and sealing step. That is, the composition supplying step may be a step of supplying an epoxy resin composition onto a laminate including a support and a semiconductor element mounted on the support, and then attaching a mold to the laminate.

[0082] This step may also be a step of supplying an epoxy resin composition to a mold used to form a molded article in the molding and sealing step, and then mounting a laminate comprising a support and a semiconductor element mounted on the support on the mold. By performing such a step, the epoxy resin composition can be supplied onto the laminate comprising a support and a semiconductor element mounted on the support.

[0083] (Molding and Encapsulating Step) The molding and encapsulating step is a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, and curing the molded body to encapsulate the semiconductor element, thereby obtaining an encapsulated body. This step may include two steps: a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body (molding step), and a step of curing the molded body obtained by the molding step to encapsulate the semiconductor element, thereby obtaining an encapsulated body (encapsulating step).

[0084] The method for forming the molded body is not particularly limited, but examples include a method in which a mold attached to a laminate is pressed toward the laminate (support), and if necessary, the inside of the mold is depressurized to fill the gap between the support and the semiconductor element with the epoxy resin composition, thereby forming a compression molded body containing the laminate and the epoxy resin composition.In this step, instead of pressing the mold toward the laminate (support), the laminate (support) may be pressed toward the mold, or the mold and the laminate (support) may be sandwiched between each other.

[0085] As a method for forming the molded article, for example, an epoxy resin composition that has been heated to a low viscosity as necessary is decompressed using a molding device, and a laminate is sealed with the epoxy resin composition, thereby obtaining a molded article.

[0086] When the molded body is cured to encapsulate the semiconductor element, the epoxy resin composition may be cured by heating. The curing temperature is not particularly limited, but is preferably, for example, 110 to 200°C, and more preferably 120 to 150°C. The curing time is not particularly limited, but is, for example, preferably 30 minutes to 7 hours, more preferably 1 to 6 hours, even more preferably 1 to 4 hours, and particularly preferably 1 to 2 hours.

[0087] (Grinding Process) The grinding process is a process of polishing the encapsulated body obtained by the molding and encapsulating process, and more specifically, is a process of grinding the surface of the encapsulated body on the semiconductor element side in order to flatten and thin the encapsulated body, and to expose a part of the semiconductor element as needed. The grinding method is not particularly limited, and commercially available grinding wheels and grinding devices can be used.

[0088] (Singulation Process) The singulation process is a process for singulating the sealed body obtained in the molding and sealing process or the sealed body ground in the grinding process. The singulation process may be a process for singulating the sealed body after removing it from the mold. In the singulation process, gaps between the plurality of semiconductor elements mounted on the support and sealed with the cured product of the epoxy resin composition are cut using a means such as a dicing blade or a laser to obtain a semiconductor device. The method of singulation is not particularly limited, and a commercially available singulation device can be used.

[0089] Hereinafter, an embodiment of a method for manufacturing a semiconductor device will be described with reference to FIGS. 1 and 2, but the present invention is not limited to this.

[0090] FIG. 1 shows one embodiment of the semiconductor device manufacturing method of the present invention. This embodiment will be described below with reference to FIG. A semiconductor element 1 having solder bumps 2 on one side is mounted on a support 3, and a laminate 4 containing the semiconductor element 1, solder bumps 2, and support 3 in this order is prepared (laminate preparation step (a)). An epoxy resin composition 5 is supplied onto the semiconductor element 1 of the laminate 4 using a syringe 6, and then a mold 7 is attached (composition supply steps (b) and (c)). In this step, a release film may be provided on the surface of the mold 7 facing the laminate 4. The release film is positioned to prevent contact between the mold 7 and the epoxy resin composition 5 and also to facilitate removal of the encapsulant 9 from the mold 7 in step (f) described below. Note that the release film is not shown. The attached mold 7 is then pressed toward the support 3, and the pressure inside the mold 7 is reduced as necessary to form a compression-molded product 8 containing the laminate 4 and the epoxy resin composition 5 (molding step (d)). In this step, instead of pressing the mold 7 toward the support 3, the support 3 may be pressed toward the mold 7, or the mold 7 and the support 3 may be narrowed relative to each other. In this step, the epoxy resin composition 5 is filled into the gap between the support 3 and the semiconductor element 1 to form a compression-molded body 8. The compression-molded body 8 is thermally cured to seal the semiconductor element 1, thereby forming a sealed body 9 (sealing step (e)). After removing the mold 7, the sealed body 9 including the semiconductor element 1 is divided into individual pieces (singulation steps (f) and (g)).

[0091] FIG. 2 shows another embodiment of the semiconductor device manufacturing method of the present invention. This embodiment will be described below with reference to FIG. A semiconductor element 11 having solder bumps 12 on one side is mounted on a support 13, and a laminate 14 including the semiconductor element 11, solder bumps 12, and support 13 in this order is prepared (laminate preparation step (a)). An epoxy resin composition 15 is supplied to a mold 17 using a syringe 16, and the laminate 14 is then attached to the mold (composition supply steps (b) and (c)). In this step, a release film may be provided on the surface of the mold 17 onto which the epoxy resin composition 15 is supplied. That is, in this step, (1) the epoxy resin composition 15 may be supplied to the surface of the mold 17 that is provided with the release film, or (2) the epoxy resin composition 15 may be supplied onto the release film, and the release film may then be placed on the mold 17. The release film is arranged to prevent contact between the mold 17 and the epoxy resin composition 15, and also to facilitate removal of the encapsulated body 19 from the mold 17 in the step (f) described below. The release film is not shown. Next, the pressure inside the mold 17 is reduced, and a compression-molded body 18 containing the laminate 14 and the epoxy resin composition 15 is formed (molding step (d)). In this step, the epoxy resin composition 15 fills the gap between the support 13 and the semiconductor element 11, forming the compression-molded body 18. The compression-molded body 18 is thermally cured to encapsulate the semiconductor element 11, thereby forming the encapsulated body 19 (encapsulating step (e)). After the mold 17 is removed, the encapsulated body 19 containing the semiconductor element is singulated (singulation steps (f) and (g)).

[0092] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0093] The epoxy resin compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were prepared by mixing the epoxy resin (A), the curing accelerator (B), the inorganic filler (C), and, if necessary, the curing agent (D) so as to obtain the blending ratios shown in Table 1. The numerical values ​​for each component in Table 1 indicate parts by mass.

[0094] Each component in Table 1 is explained below. Epoxy resin (A) EP-3950L (product name): aminophenol-type epoxy resin, epoxy equivalent 95 g / eq, liquid at 25°C, manufactured by ADEKA Corporation AER4001 (product name): oxazolidone ring-containing epoxy resin, epoxy equivalent 292 g / eq, liquid at 25°C, manufactured by Asahi Kasei Corporation AER4004 (product name): oxazolidone ring-containing epoxy resin, epoxy equivalent 395 g / eq, liquid at 25°C, manufactured by Asahi Kasei Corporation HP-4032D (product name): naphthalene-type epoxy resin, epoxy equivalent 144 g / eq, liquid at 25°C, manufactured by DIC Corporation FAE-2500 (product name): trisphenolmethane-type epoxy resin, epoxy equivalent 214 g / eq, liquid at 25°C, manufactured by Nippon Kayaku Co., Ltd. EPPN-501HY (product name): Trisphenolmethane type epoxy resin, epoxy equivalent 169 g / eq, liquid at 25°C, manufactured by Nippon Kayaku Co., Ltd. YDF870GS (product name): Bisphenol F type epoxy resin, epoxy equivalent 163 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. YX7400N (product name): Aliphatic epoxy resin, epoxy equivalent 440 g / eq, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation. Curing accelerator (B) 2MZA-PW (product name): 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, manufactured by Shikoku Chemicals Corporation. 2E4MZ (product name): 2-ethyl-4-methyl-imidazole, manufactured by Shikoku Chemicals Corporation. Inorganic filler (C) YA050C-SM1 (product name): Silicon dioxide surface-treated with 3-methacryloxypropyltrimethoxysilane, average particle size 0.05 μm, manufactured by Admatechs Co., Ltd. SE1050-SMO (product name): Silicon dioxide surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.3 μm, manufactured by Admatechs Co., Ltd. Curing agent (D) MEH-8005 (product name): Phenol-based curing agent, hydroxyl equivalent 139 to 143 g / eq, manufactured by Meiwa Chemical Industry Co., Ltd. HN-5500 (product name): Acid anhydride-based curing agent, manufactured by Resonac Co., Ltd.

[0095] (Evaluation 1: Evaluation of Delamination) A 600 μm-thick, 20 mm square chip was fixed with adhesive to a circular silicon wafer with a diameter of 300 mm and a thickness of 300 μm to obtain a substrate. Using a molding machine (WCM-300, manufactured by Apic Yamada Co., Ltd.), the epoxy resin compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were applied to the substrate. The substrate coated with the epoxy resin composition was molded at 120°C for 600 seconds to a diameter of 292 mm and a thickness of 500 μm. The molded product was heat-cured at 150°C for 60 minutes, and then the presence or absence of delamination on the chip side was observed using a cross-sectional scanning electron microscope (SEM). The observation results were evaluated according to the following criteria. The results are listed in the "Delamination" section of Table 1. A: No delamination was observed on any of the chip side surfaces. B: Delamination was observed on some of the chip side surfaces. C: Delamination was observed on all of the chip side surfaces.

[0096] Figure 3(A) is a cross-sectional SEM image of the chip side surface of Example 1, in which no delamination was observed on any of the chip side surfaces. Figure 3(B) is a cross-sectional SEM image of the chip side surfaces of Examples 6 and 7, from left to right, in which delamination was observed on some of the chip side surfaces. Figure 3(C) is a cross-sectional SEM image of the chip side surface of Comparative Example 1, in which delamination was observed on the entire chip side surface.

[0097] (Evaluation 2: Warpage Measurement) A 600 μm thick, 20 mm square chip was fixed with adhesive onto a circular silicon wafer with a diameter of 300 mm and a thickness of 300 μm to obtain a substrate. Using a molding device (Apic Yamada Corporation, WCM-300), the epoxy resin compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were applied to the substrate. The substrate coated with the epoxy resin composition was molded at 120°C, with a mold cure time of 400 seconds and a clamping force of 250 kN, followed by post-mold cure (PMC) at 150°C for 1 hour. The resulting sealed body was allowed to stand for 1 hour immediately after PMC, and then the amount of warpage at 25°C was measured using a shadow moiré device (Akrometrix, AXP 2.0-DFP2). The highest point was recorded as the amount of warpage when the sample was placed on a horizontal table with the cured surface facing up. The results are shown in Table 1 under "Warpage (μm)".

[0098]

[0099] Variations of the invention according to the present disclosure are described below. [Appendix 1] An epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), wherein the epoxy resin (A) comprises an aminophenol-type epoxy resin (A1) and a low-shrinkage epoxy resin (A2). [Appendix 2] The epoxy resin composition according to Appendix 1, wherein the epoxy resin (A) further comprises an aliphatic epoxy resin (A3). [Appendix 3] The epoxy resin composition according to Appendix 1 or Appendix 2, wherein the low-shrinkage epoxy resin (A2) comprises at least one selected from the group consisting of oxazolidone ring-containing epoxy resins, naphthalene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and trisphenolmethane-type epoxy resins, or comprises an oxazolidone ring-containing epoxy resin, or comprises a naphthalene-type epoxy resin. [Appendix 4] The epoxy resin composition according to any one of Appendices 1 to 3, wherein the content of the epoxy resin (A) relative to the epoxy resin composition (100% by mass) is 3 to 60% by mass, 6 to 50% by mass, 9 to 40% by mass, or 12 to 35% by mass. [Appendix 5] The epoxy resin composition according to any one of Appendices 1 to 4, wherein the content of the aminophenol-type epoxy resin (A1) relative to the epoxy resin (A) (100% by mass) is 20 to 80% by mass, 24 to 70% by mass, 28 to 60% by mass, or 30 to 55% by mass. [Appendix 6] The epoxy resin composition according to any one of Appendices 1 to 5, wherein the content of the low-shrinkage epoxy resin (A2) relative to the epoxy resin (A) (100% by mass) is 3 to 80% by mass, 5 to 70% by mass, 8 to 60% by mass, or 8 to 55% by mass. [Appendix 7] The epoxy resin composition according to any one of Appendices 2 to 6, wherein the content of the aliphatic epoxy resin (A3) relative to the epoxy resin (A) (100% by mass) is 10 to 60% by mass, 15 to 50% by mass, or 20 to 40% by mass. [Appendix 8] The epoxy resin composition according to any one of Appendices 1 to 7, wherein the content of the low-shrinkage epoxy resin (A2) relative to the aminophenol-type epoxy resin (A1) (100% by mass) is 1 to 200% by mass, 3 to 150% by mass, 5 to 140% by mass, 10 to 130% by mass, or 15 to 130% by mass.[Appendix 9] The epoxy resin composition according to any one of Appendices 1 to 8, comprising, as the curing accelerator (B), at least one selected from the group consisting of imidazole curing accelerators, tertiary amine curing accelerators, and phosphorus curing accelerators, or comprising an imidazole curing accelerator. [Appendix 10] The epoxy resin composition according to any one of Appendices 1 to 9, wherein the content of the curing accelerator (B) is 0.01 to 5 mass%, 0.05 to 4 mass%, 0.1 to 3 mass%, 0.2 to 2 mass%, or 0.5 to 2 mass%. [Appendix 11] The epoxy resin composition according to any one of Appendices 1 to 10, comprising, as the inorganic filler (C), at least one selected from the group consisting of silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, lime sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and inorganic particles having their surfaces treated. [Appendix 12] The epoxy resin composition according to any one of Appendices 1 to 11, wherein the inorganic filler (C) has been surface-treated with a coupling agent having an epoxy group, a (meth)acryloyl group, or an amino group (particularly a phenylamino group). [Appendix 13] The epoxy resin composition according to any one of Appendices 1 to 12, wherein the content of the inorganic filler (C) is 30 to 95 mass%, 50 to 90 mass%, 60 to 88 mass%, 70 to 86 mass%, 72 to 82 mass%, 74 to 81 mass%, or 78 to 81 mass%. [Appendix 14] The epoxy resin composition according to any one of Appendices 1 to 13, wherein the average particle size of the inorganic filler (C) is 1 nm to 15 μm, 5 nm to 10 μm, 10 nm to 5 μm, 20 nm to 1 μm, or 30 nm to 0.5 μm. [Appendix 15] The epoxy resin composition according to any one of Appendices 1 to 14, wherein the inorganic filler (C) comprises an inorganic filler (C1) having an average particle size of 100 nm to 10 μm and an inorganic filler (C2) having an average particle size of 1 nm or more but less than 100 nm. [Appendix 16] The epoxy resin composition according to Appendix 15, wherein the inorganic filler (C1) has an average particle size of 200 nm or more, or 250 nm or more.[Appendix 17] The epoxy resin composition according to any one of Appendices 15 and 16, wherein the inorganic filler (C1) has an average particle size of 5 μm or less, 1 μm or less, or 0.5 μm or less. [Appendix 18] The epoxy resin composition according to any one of Appendices 15 to 17, wherein the inorganic filler (C2) has an average particle size of 5 nm or more, or 10 nm or more. [Appendix 19] The epoxy resin composition according to any one of Appendices 15 to 18, wherein the inorganic filler (C2) has an average particle size of 80 nm or less, or 60 nm or less. [Appendix 20] The epoxy resin composition according to any one of Appendices 1 to 19, further comprising a curing agent (D). [Appendix 21] The epoxy resin composition according to Appendices 20, wherein the curing agent (D) comprises at least one selected from the group consisting of an amine-based curing agent, an acid anhydride-based curing agent, and a phenol-based curing agent, or comprises an acid anhydride-based curing agent and / or a phenol-based curing agent. [Appendix 22] The epoxy resin composition according to Appendices 20 or 21, wherein the content of the curing agent (D) is 0.01 to 5 mass%, 0.05 to 4 mass%, 0.1 to 3 mass%, 0.2 to 2 mass%, or 0.5 to 2 mass%. [Appendix 23] The epoxy resin composition according to any one of Appendices 20 to 22, wherein the content of the curing agent (D) relative to the epoxy resin composition (100 mass%) excluding the inorganic filler (C) is 0.1 to 30 mass%, 0.5 to 20 mass%, 1 to 15 mass%, or 2 to 15 mass%. [Appendix 24] The epoxy resin composition according to any one of Appendices 1 to 23, which is a liquid compression molding material. [Appendix 25] A cured product of the epoxy resin composition according to any one of Appendices 1 to 24. [Appendix 26] A semiconductor device comprising the cured product according to Appendices 25. [Appendix 27] A semiconductor device comprising: a support, a semiconductor element mounted on the support, and the cured product encapsulating the semiconductor element according to Appendix 25. [Appendix 28] A method for manufacturing a semiconductor device, comprising the steps of: supplying the epoxy resin composition according to any one of Appendixes 1 to 24 onto a laminate comprising a support and the semiconductor element mounted on the support; filling a gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, and curing the molded body to encapsulate the semiconductor element, thereby obtaining a sealed body.[Supplementary Note 29] The method for manufacturing a semiconductor device according to Supplementary Note 28, further comprising the step of polishing the sealing body.

[0100] REFERENCE SIGNS LIST 1 Semiconductor element 2 Solder bump 3 Support 4 Laminate 5 Epoxy resin composition 6 Syringe 7 Mold 8 Compression molded body 9 Sealed body 11 Semiconductor element 12 Solder bump 13 Support 14 Laminate 15 Epoxy resin composition 16 Syringe 17 Mold 18 Compression molded body 19 Sealed body

Claims

1. An epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), wherein the epoxy resin (A) comprises an aminophenol-type epoxy resin (A1) and a low-shrinkage epoxy resin (A2).

2. The epoxy resin composition according to claim 1, wherein the content of the aminophenol-type epoxy resin (A1) relative to the epoxy resin (A) is 28 to 60 mass %.

3. The epoxy resin composition according to claim 1 or 2, wherein the content of the low-shrinkage epoxy resin (A2) relative to the aminophenol-type epoxy resin (A1) is 5 to 150 mass %.

4. The epoxy resin composition according to claim 1 or 2, further comprising a curing agent (D).

5. The epoxy resin composition according to claim 1 or 2, comprising, as the low-shrinkage epoxy resin (A2), at least one selected from the group consisting of oxazolidone ring-containing epoxy resins, naphthalene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and trisphenolmethane-type epoxy resins.

6. The epoxy resin composition according to claim 1 or 2, which contains an oxazolidone ring-containing epoxy resin as the low-shrinkage epoxy resin (A2).

7. The epoxy resin composition according to claim 1 or 2, which contains a naphthalene-type epoxy resin as the low-shrinkage epoxy resin (A2).

8. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) further contains an aliphatic epoxy resin (A3).

9. The epoxy resin composition according to claim 1 or 2, wherein the curing accelerator (B) comprises an imidazole curing accelerator.

10. The epoxy resin composition according to claim 4, wherein the curing agent (D) comprises an acid anhydride curing agent and / or a phenolic curing agent.

11. The epoxy resin composition according to claim 1 or 2, wherein the content of the epoxy resin (A) is 9 mass% or more.

12. The epoxy resin composition according to claim 1 or 2, wherein the content of the curing accelerator (B) relative to the epoxy resin (A) (100% by mass) is 0.5 to 15% by mass.

13. The epoxy resin composition according to claim 1 or 2, which is a liquid compression molding material.

14. A cured product of the epoxy resin composition according to claim 1 or 2.

15. A semiconductor device comprising the cured product according to claim 14.

16. A semiconductor device comprising: a support; a semiconductor element mounted on said support; and the cured product according to claim 14 that encapsulates said semiconductor element.

17. A method for manufacturing a semiconductor device, comprising the steps of: supplying the epoxy resin composition according to claim 1 or 2 onto a laminate comprising a support and a semiconductor element mounted on the support; filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body; and curing the molded body to encapsulate the semiconductor element, thereby obtaining an encapsulated body.

18. The method for manufacturing a semiconductor device according to claim 17, further comprising the step of polishing the encapsulant.

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