Epoxy resin composition, cured product, semiconductor device, and method for manufacturing a semiconductor device.

Abstract

The present invention provides an epoxy resin composition capable of reducing the occurrence of bump connection failures. It also provides a cured product of the epoxy resin composition, a semiconductor device equipped with the cured product, and a method for manufacturing the semiconductor device. Epoxy resin (A), Hardener (B), and An epoxy resin composition containing an inorganic filler (C), An epoxy resin composition comprising an inorganic filler (CX) with a top cut diameter of 3.0 μm or less as an inorganic filler (C).

Description

Technical Field

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

Background Art

[0002] In recent years, with the miniaturization, weight reduction, and high performance of electronic devices, the mounting form of semiconductors has been gradually shifting from the wire bond type to the flip chip type. A flip chip type semiconductor device has a structure in which an electrode portion on a substrate and a semiconductor element are connected via bumps. In addition, a semiconductor encapsulant called underfill is used to protect the connected semiconductor element, substrate, and bumps. This underfill is filled between the semiconductor element and the substrate, and further cures by heating to seal the semiconductor element.

[0003] From the viewpoint of protecting semiconductor elements and the like, inorganic fillers such as silica fillers are generally blended in underfill. By blending an inorganic filler into the underfill, it becomes possible to protect the bumps from stress due to deformation of the semiconductor device and impacts such as dropping, and effectively prevent poor connection between the semiconductor element and the substrate.

[0004] As methods for manufacturing silica fillers, there are mainly the combustion method and the sol-gel method. The silica filler manufactured by the combustion method has a broad particle size distribution, and the silica filler manufactured by the sol-gel method has a sharp particle size distribution. The silica filler manufactured by the combustion method contains coarse particles having a particle size larger than the target particle size, and it is known that the coarse particles contain solid particles and hollow particles (hereinafter referred to as solid particles and hollow particles, respectively) (Patent Document 1). Further, as a conventional technique, it has been reported that an epoxy resin composition containing a hollow inorganic filler as an essential component has a low dielectric constant, little warpage in a single-sided encapsulated semiconductor device using a resin substrate, and good moldability (Patent Document 2).

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-161008 [Patent Document 2] Japanese Patent Publication No. 2005-041937 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, because hollow particles are more easily deformed and softer than solid particles, the presence of hollow inorganic filler near bumps can cause deformation stress due to warping of the semiconductor device and shocks received by the device to concentrate on the bumps, sometimes resulting in bump connection failures. This phenomenon is explained using Figure 2.

[0007] Figure 2 is a magnified cross-sectional image of a encapsulant obtained by filling the gap between the semiconductor element and the substrate with underfill 11 and curing it. When an external force is applied to the encapsulant, the hollow inorganic filler 13 is easily deformed, causing stress to concentrate around the hollow inorganic filler 13. If the hollow inorganic filler 13 is located near the bump 12, stress strain may occur between the bump 12 and the filler 13, potentially leading to delamination. As a result, problems such as cracks forming between the bump 12 and the solder, or between the bump 12 and the substrate, can occur. This problem can be attributed to the miniaturization of the semiconductor element itself and the narrowing of the gap between the semiconductor element and the substrate, which are associated with the miniaturization of flip-chip semiconductor devices.

[0008] Therefore, an object of the present invention is to provide an epoxy resin composition capable of reducing the occurrence of bump connection failures. Another object is to provide a cured product of the epoxy resin composition, a semiconductor device equipped with the cured product, and a method for manufacturing the semiconductor device. [Means for solving the problem]

[0009] The inventors of this invention, after diligent research to achieve the above objectives, have found that the above problems can be solved by using a composition having a specific configuration. This invention was completed based on these findings.

[0010] In other words, in the present invention, Epoxy resin (A), Hardener (B), and An epoxy resin composition containing an inorganic filler (C), The present invention provides an epoxy resin composition comprising an inorganic filler (CX) having a top cut diameter of 3.0 μm or less as an inorganic filler (C).

[0011] Furthermore, in this invention, Epoxy resin (A), Hardener (B), and An epoxy resin composition containing an inorganic filler (C), The present invention provides an epoxy resin composition in which the number of hollow particles derived from the inorganic filler (C) in the cross-section of the cured product (50 μm vertically × 2 cm horizontally) is one or less.

[0012] The epoxy resin composition described above preferably contains an amine-based curing agent (B3) as the curing agent (B).

[0013] The epoxy resin composition described above preferably contains an aromatic amine as the curing agent (B).

[0014] The above epoxy resin composition includes an inorganic filler (CX) with a top cut diameter of 3.0 μm or less as an inorganic filler (C). It is preferable that the inorganic filler (CX) is an inorganic filler obtained by a combustion method.

[0015] The content of the curing agent (B) relative to the epoxy resin composition (100% by mass) is preferably 3% by mass or more.

[0016] The epoxy resin composition described above preferably does not contain styrene-butadiene compounds and PMMA-PnBA block polymers.

[0017] It is preferable that the above epoxy resin composition does not contain phosphoric acid or a phosphoric acid polyester.

[0018] As the epoxy resin (A), it is preferable not to contain a silicone resin having two or more epoxy groups in one molecule.

[0019] The content of the inorganic filler (C) with respect to the above epoxy resin composition (100% by mass) is preferably 30 to 80% by mass.

[0020] The inorganic filler (C) preferably contains an inorganic filler (C2) having an average particle diameter of 1 nm or more and less than 100 nm.

[0021] In the above epoxy resin composition, the content of the inorganic filler (CX) with respect to the inorganic filler (C) (100% by mass) is preferably 30% by mass or more.

[0022] The epoxy resin (A) preferably contains at least one selected from bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and 1,4-glycidylcyclohexane.

[0023] The above epoxy resin composition preferably further contains core-shell type rubber particles (D).

[0024] The viscosity (10 rpm) at 25°C is preferably 60 Pa·s or less.

[0025] The above epoxy resin composition is preferably for semiconductor encapsulation.

[0026] In the present invention, a cured product of the above epoxy resin composition is also provided.

[0027] In the present invention, a substrate, A semiconductor element arranged on the above substrate, The cured material that encases the above semiconductor element, We also provide semiconductor devices equipped with these features.

[0028] In this invention, A step of filling the gap between the substrate and the semiconductor element placed on the substrate with the epoxy resin composition, A step of heating and curing the epoxy resin composition, We also provide a method for manufacturing a semiconductor device that includes this device. [Effects of the Invention]

[0029] The epoxy resin composition of the present invention can reduce the occurrence of bump connection failures. Furthermore, semiconductor devices equipped with a cured product of the above epoxy resin composition exhibit high reliability because bump connection failures are less likely to occur. [Brief explanation of the drawing]

[0030] [Figure 1] (a) to (c) are diagrams illustrating "Evaluation 2: Gap Filling Test" in the example. [Figure 2] This is a magnified cross-sectional image of the sealing material. [Figure 3] This is a cross-sectional image of the cured product of Example 1 in Evaluation 3. [Figure 4] This is a cross-sectional image of the cured product of Example 4 in Evaluation 3. [Modes for carrying out the invention]

[0031] (Epoxy resin composition) The epoxy resin composition according to the first embodiment of the present invention comprises an epoxy resin (A), a curing agent (B), and an inorganic filler (C), characterized in that the inorganic filler (C) includes an inorganic filler (CX) having a top cut diameter of 3.0 μm or less.

[0032] The epoxy resin composition according to the second embodiment of the present invention comprises an epoxy resin (A), a curing agent (B), and an inorganic filler (C), and is characterized in that the number of hollow particles derived from the inorganic filler (C) in the cross-section of the cured product (50 μm vertically × 2 cm horizontally) is one or less.

[0033] • Epoxy resin (A) The above epoxy resin composition, by containing epoxy resin (A), can form a cured product with high electrical insulation properties. The number of epoxy groups in epoxy resin (A) is not particularly limited as long as it is one or more, but it is preferable that it is two or more (i.e., a polyfunctional type epoxy resin). Epoxy resin (A) can be used alone or in combination of two or more types.

[0034] The epoxy resin (A) may be liquid or solid at room temperature (25°C), but from the viewpoint of the viscosity of the epoxy resin composition, it is preferable that it be liquid. Even if it is a solid epoxy resin, it can preferably be used if it becomes liquid as a mixture when used in combination with a liquid epoxy resin.

[0035] The epoxy resin (A) is not particularly limited, but examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bixylenol type epoxy resin, cyclohexane type epoxy resin (e.g., 1,4-glycidylcyclohexane), dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, Examples include glycidylamine-type epoxy resins (glycidylamine-type epoxy resins without aromatic structures or glycidylamine-type epoxy resins with aromatic structures), glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiroring-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.

[0036] From the viewpoint of reducing the occurrence of bump connection failures, the epoxy resin composition described above preferably contains at least one selected from bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and 1,4-glycidylcyclohexane as epoxy resin (A).

[0037] The above epoxy resin composition may contain a silicone-modified epoxy resin (a silicone resin having two or more epoxy groups in one molecule), but it is preferable that it is not included from the viewpoint of component compatibility in the composition.

[0038] 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" (both liquid 1,4-glycidylcyclohexane) from Nippon Steel Chemical & Material Co., Ltd.; "HP-4032," "HP-4032D," and "HP-4032SS" (all naphthalene type epoxy resins) from DIC Corporation; and "jER828US" and "jER828EL" from Mitsubishi Chemical Corporation. (All are bisphenol A type epoxy resins), "jER806", "jER807" (All are bisphenol F type epoxy resins), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD" (All are aminophenol type epoxy resins), "YX7400N" (aliphatic epoxy resin / polytetramethylene glycol diglycidyl ether); "Epogosei PT" (polytetramethylene glycol diglycidyl ether) from Yokkaichi Gosei Co., Ltd.; "ZX105" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd. 9 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) and "EX171" (lauryl alcohol (EO) 15 glycidyl ether) manufactured by Nagase ChemteX Corporation; "ADEKA Resin EP4005" (bisphenol A type epoxy resin containing polypropylene glycol structure), "EP-3950L", and "EP-3980S" (both glycidylamine type epoxy resins) manufactured by ADEKA Corporation; "AER9000" (PO-modified bisphenol F) manufactured by Asahi Kasei Corporation Examples include oxazolidone ring-containing epoxy resins (e.g., "AER4001", "AER4004", "AER4152"); "DER852", "DER858" (both oxazolidone ring-containing epoxy resins) from Dow Chemical Ltd.; "FAE-2500", "EPPN-501HY" (both trisphenolmethane-type epoxy resins) and "RE410S" (bisphenol A-type epoxy resin) from Nippon Kayaku Co., Ltd.; and "Celoxide 2021P" (alicyclic epoxy resin) from Daicel Corporation.

[0039] Specific examples of solid epoxy resins include DIC Corporation's "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both 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 dicyclopentadi (Naphthylene ether type epoxy resin), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (all naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenolmethane type epoxy resin), "NC-7000-L" (naphthol novolac type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", "NC-310 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. Examples include "PG-100" and "CG-500" from Osaka Gas Chemical 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) from Mitsubishi Chemical Corporation.

[0040] The epoxy equivalent of epoxy resin (A) is not particularly limited, but is preferably 30 to 800 g / eq, more preferably 40 to 600 g / eq, even more preferably 50 to 400 g / eq, even more preferably 60 to 300 g / eq, and most preferably 80 to 200 g / eq.

[0041] The content of epoxy resin (A) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. Also, is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less. When the content of epoxy resin (A) is within the above range, the epoxy resin composition tends to have excellent injectability.

[0042] • Hardener (B) The curing agent (B) is not particularly limited, but examples include phenolic curing agents (B1), acid anhydride curing agents (B2), amine curing agents (B3), and imidazole curing agents (B4). From the viewpoint of reducing the occurrence of bump connection failures, the epoxy resin composition preferably contains an amine curing agent (B3) as the curing agent (B). The curing agent (B) can be used alone or in combination of two or more types.

[0043] The phenolic curing agent (B1) may be any monomer, oligomer, or polymer having a phenolic hydroxyl group. Examples include phenol novolac resin, alkylated phenol novolac resin, allylated phenol novolac resin, cresol novolac resin, phenol aralkyl resin (e.g., resin containing a phenylene skeleton and / or biphenylene skeleton), naphthol aralkyl resin, triphenolmethane resin, and dicyclopentadiene type phenolic resin. The phenolic curing agent (B1) may be liquid or solid at room temperature (25°C), but it is preferable to be liquid from the viewpoint of workability in epoxy resin compositions. The phenolic curing agent (B1) may be used alone or in combination of two or more types.

[0044] Acid anhydride-based curing agents (B2) are curing agents having one or more acid anhydride groups in one molecule. Acid anhydride-based curing agents (B2) include acid anhydrides, aqueous additives of acid anhydrides, and modified acid anhydrides, and examples include phthalic anhydride-based curing agents, succinic anhydride-based curing agents, glutaric anhydride-based curing agents, etc. Acid anhydride-based curing agents (B2) can be used individually or in combination of two or more types.

[0045] The above-mentioned phthalic anhydride-based curing agent is a curing agent having a skeleton derived from phthalic anhydride within its molecule. The above-mentioned phthalic anhydride-based curing agent is not particularly limited, but examples include phthalic anhydrides which may have substituents (preferably hydrocarbon groups) such as trimellitic anhydride, pyromellitic anhydride, and bensophenonetetracarboxylic dianhydride; and hydrogenated phthalic anhydrides which may have substituents (preferably hydrocarbon groups, more preferably alkyl or alkenyl groups) such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and nadic anhydride. The succinic anhydride-based curing agent described above is not particularly limited, but examples include succinic anhydrides which may have substituents (preferably hydrocarbon groups, more preferably alkyl or alkenyl groups). The glutaric anhydride-based curing agent described above is not particularly limited, but examples include glutaric anhydrides which may have substituents (preferably hydrocarbon groups, more preferably alkyl or alkenyl groups).

[0046] Examples of amine-based curing agents (B3) include aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-methylenebis(2-ethylaniline), diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. Amine-based curing agents (B3) can be used individually or in combination of two or more.

[0047] Examples of imidazole-based curing agents (B4) include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Microencapsulated imidazole-based curing agents (B4) are also available. Imidazole-based curing agents (B4) can be used individually or in combination of two or more types.

[0048] The curing agent equivalent (molecular weight per functional group of the curing agent) of curing agent (B) is not particularly limited, but is preferably 10 to 300 g / eq, more preferably 20 to 200 g / eq, and even more preferably 30 to 100 g / eq.

[0049] The amount of curing agent (B) is not particularly limited, but it is preferably such that the stoichiometric equivalent ratio (curing agent equivalent / epoxy group equivalent) with the epoxy resin (A) is, for example, 0.5 to 1.5, and more preferably 0.8 to 1.2.

[0050] The content of the curing agent (B) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 6% by mass or more, and particularly preferably 8% by mass or more. Alternatively, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. When the content of the curing agent (B) is within the above range, curability and adhesive reliability tend to improve.

[0051] The content of the curing agent (B) relative to the epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more. Alternatively, it is preferably 100% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the content of the curing agent (B) is within the above range, the curability and adhesive reliability tend to improve.

[0052] ·Inorganic filler (C) The inorganic filler (C) is not particularly limited, but it is preferable that it (1) has the property of suppressing volume shrinkage (curing shrinkage) caused by the curing reaction of the epoxy resin composition, (2) has the property of suppressing volume change (thermal shrinkage) due to heating of the cured product, that is, has the effect of lowering the coefficient of linear expansion when added, or (3) has both of the above properties. One type of inorganic filler (C) can be used alone, or two or more types can be used in combination.

[0053] 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 of these materials with treated surfaces. Among these, silica is preferred from the viewpoint of achieving a high filler content. Inorganic fillers (C) can be used individually or in combination of two or more types.

[0054] 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 surface treatment of the inorganic filler (C), one of the coupling agents can be used alone, or two or more can be used in combination.

[0055] The shape of the inorganic filler (C) is not particularly limited, but examples include spherical (perfectly spherical, nearly spherical, etc.), polyhedral, rod-shaped (cylindrical, prismatic, etc.), plate-shaped, flake-shaped, and irregularly shaped. Among these, a spherical shape is preferred from the viewpoint of achieving a high filling capacity.

[0056] From the viewpoint of reducing the occurrence of bump connection failures, it is preferable to use an inorganic filler (C) with a top cut diameter of 3.0 μm or less. Such an inorganic filler is referred to as inorganic filler (CX). Examples of inorganic filler (CX) include inorganic fillers obtained by combustion, inorganic fillers obtained by sol-gel, and inorganic fillers obtained by sedimentation, but inorganic fillers obtained by combustion are preferred. When the inorganic filler (CX) is obtained by combustion, the occurrence of bump connection failures tends to be further reduced. As for the inorganic filler (CX) obtained by combustion, silica obtained by combustion is more preferable. The surface of the silica may be treated.

[0057] Inorganic packing material (CX) is obtained by passing the particles through a sieve after a classification process to remove coarse particles. The classification process can be carried out either wet or dry. The top cut diameter refers to the size (diameter) of the sieve opening when the inorganic packing material, after the classification process, is dispersed in a dispersion medium (selected from organic solvents such as water, alcohol, or ketones) and passed through the sieve. In other words, inorganic packing material (CX) can be described as an inorganic packing material obtained by passing the particles obtained through the classification process, dispersed in a dispersion medium, through a sieve with a mesh size (diameter) of 3.0 μm or less.

[0058] Specific examples of inorganic fillers (C) include "SE203G-SEJ," "SE101G-SEO," "SE2050-SEJ," and "SE1050-SEO" manufactured by Admatex Co., Ltd. Of these, "SE203G-SEJ" and "SE101G-SEO" are silica with a top cut diameter of 3 μm (i.e., equivalent to inorganic filler (CX)), while "SE2050-SEJ" and "SE1050-SEO" are silica with a top cut diameter of 5 μm.

[0059] The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 1 nm to 10 μm, more preferably 5 nm to 5 μm, even more preferably 10 nm to 3 μm, and particularly preferably 30 nm to 1 μm. When the average particle size of the inorganic filler (C) is within the above range, the epoxy resin composition tends to have high injectability even in narrow gaps. In this specification, the method for measuring the average particle size of the inorganic filler (C) is not particularly limited, but can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0060] The epoxy resin composition described above may contain two or more inorganic fillers with different average particle sizes for the purpose of adjusting viscosity. Specifically, it is preferable that the inorganic filler (C) includes an inorganic filler (C1) with an average particle size of 0.1 to 10 μm and an inorganic filler (C2) with an average particle size of 1 nm or more and less than 100 nm. The average particle size of inorganic filler (C1) is preferably 0.15 to 5 μm, more preferably 0.2 to 3 μm, even more preferably 0.25 to 2 μm, and particularly preferably 0.3 to 1 μm. The average particle size of inorganic filler (C2) is preferably 3 to 80 nm, more preferably 5 to 60 nm, even more preferably 6 to 50 nm, and particularly preferably 8 to 40 nm.

[0061] The epoxy resin composition described above may contain silica obtained by the sol-gel method, but since such silica has the characteristic of easily adsorbing moisture, it is preferable to omit it from the viewpoint of suppressing the hygroscopicity of the cured product.

[0062] The content of inorganic filler (C) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Also, is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, and particularly preferably 60% by mass or less. When the content of inorganic filler (C) is within the above range, the epoxy resin composition tends to have excellent injectability and the occurrence of bump connection failures is reduced.

[0063] The content of inorganic filler (C) relative to epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 100% by mass or more, even more preferably 120% by mass or more, even more preferably 140% by mass or more, and particularly preferably 150% by mass or more. Also, is preferably 600% by mass or less, more preferably 500% by mass or less, even more preferably 400% by mass or less, even more preferably 350% by mass or less, even more preferably 300% by mass or less, even more preferably 250% by mass or less, and particularly preferably 200% by mass or less. When the content of inorganic filler (C) is within the above range, the epoxy resin composition tends to have excellent injectability and the occurrence of bump connection failures is reduced.

[0064] The content of inorganic filler (CX) relative to inorganic filler (C) (100% by mass) in the above epoxy resin composition 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 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more. When the content of inorganic filler (CX) is within the above range, the epoxy resin composition tends to have excellent injectability and the occurrence of bump connection failures is further reduced.

[0065] The content of inorganic filler (C2) relative to inorganic filler (C) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Also, is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 7.5% by mass or less, even more preferably 6% by mass or less, even more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3% by mass or less. When the content of inorganic filler (C2) is within the above range, the epoxy resin composition tends to have excellent injectability and the occurrence of bump connection failures is further reduced.

[0066] • Core-shell type rubber particles (D) The epoxy resin composition described above may contain core-shell type rubber particles (D). Core-shell type rubber particles (D) are rubber particles composed of a core portion and one or more shell layers covering the core portion. By including core-shell type rubber particles (D) in the epoxy resin composition, the injectability of the epoxy resin composition can be improved and crack formation in the cured product can be suppressed. Core-shell type rubber particles (D) can be used individually or in combination of two or more types.

[0067] In core-shell type rubber particles (D), examples of materials constituting the core include silicone-based rubber such as polydimethylsiloxane, butadiene-based rubber, styrene-based rubber, acrylic-based rubber, polyolefin-based rubber, and silicone / acrylic-based composite rubber.

[0068] Materials constituting the shell layer include monomers having epoxy groups and monomers not having epoxy groups. That is, the shell layer contains monomers having epoxy groups and / or monomers not having epoxy groups as constituent units. Examples of monomers having epoxy groups include glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate, glycidyl methyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and glycidyl group-containing vinyl monomers such as allyl glycidyl ether. Examples of monomers not having epoxy groups include unsaturated carboxylic acids, (meth)acrylates not having epoxy groups, aromatic vinyl compounds, and vinyl cyanide compounds. Examples of unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, crotonic acid, and maleic anhydride. Examples of (meth)acrylates not having epoxy groups include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. 1-5 Examples include alkyl (meth)acrylates. Examples of the above aromatic vinyl compounds include vinylbenzenes such as styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene. Examples of the above vinyl cyanide compounds include acrylonitriles and methacrylonitriles.

[0069] The average particle size of the core-shell type rubber particles (D) is not particularly limited, but is preferably 0.03 to 1.0 μm, more preferably 0.04 to 0.8 μm, and even more preferably 0.05 to 0.7 μm. A method for measuring the average particle size of the core-shell type rubber particles (D) is, for example, to observe a cross-section of a cured product obtained by curing the epoxy resin composition using a scanning electron microscope (SEM). Specifically, any 100 μm 2 By observing the area using SEM, the particle size of the confirmed core-shell type rubber particles (D), or the diameter of the recess from which the core-shell type rubber particles (D) have fallen out, can be arbitrarily selected at 10 locations, and the average value of these values ​​can be taken as the average particle size of the core-shell type rubber particles (D).

[0070] The content of core-shell type rubber particles (D) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less. Also, 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.

[0071] • Coupling agent (E) The epoxy resin composition described above may contain a coupling agent (E). Examples of coupling agents (E) include silane coupling agents such as vinyl, glycidoxy, (meth)acrylic, amino, mercapto, or imidazole; titanium coupling agents such as alkoxide, chelate, or acylate; and long-chain spacer type coupling agents such as glycidoxyoctyltrimethoxysilane or methacrylooctyltrimethoxysilane. The coupling agent (E) can be used alone or in combination of two or more types.

[0072] Examples of the silane coupling agents mentioned above include 3-isocyanatetopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

[0073] The content of the coupling agent (E) in 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 0.15% by mass or more, and particularly preferably 0.2% by mass or more. Also, is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less.

[0074] • Curing accelerator (F) The epoxy resin composition described above may contain a curing accelerator (F). The curing accelerator (F) is not particularly limited, but examples include imidazole-based curing accelerators (F1), tertiary amine-based curing accelerators (F2), phosphorus-based curing accelerators (F3), and dicyandiamide. From the viewpoint of improving reflow resistance, the epoxy resin composition preferably contains a tertiary amine-based curing accelerator (F2), a phosphorus-based curing accelerator (F3), and dicyandiamide as the curing accelerator (F), and more preferably contains dicyandiamide. The curing accelerator (F) can be used alone or in combination of two or more types.

[0075] Examples of imidazole-based curing accelerators (F1) include imidazole compounds and their derivatives such as 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, and isocyanuric acid adducts of 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"), isocyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product names "2MA-OK"), "2MZ-OK", and "2PHZ", all manufactured by Shikoku Chemicals, Inc. In addition, encapsulated imidazoles, such as microencapsulated imidazoles and epoxy adduct imidazoles, 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 Corporation), as well as "PN-23J", "PN-40J", and "PN-50" (manufactured by Ajinomoto Fine Techno Co., Ltd.), and "FXR-1121" (manufactured by Fuji Kasei Kogyo Co., Ltd.).

[0076] Examples of tertiary amine-based curing accelerators (F2) 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 formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,8-diazabicyclo[5.4.0]undecene, and formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]nonene.

[0077] Examples of phosphorus-based curing accelerators (F3) include phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium-tetraphenylborate, triphenylphosphine-triphenylborane, and 1,2-bis-(diphenylphosphine-no)ethane.

[0078] The content of the curing accelerator (F) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. Also, is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0079] Other ingredients (G) The epoxy resin composition described above may contain components other than epoxy resin (A), curing agent (B), inorganic filler (C), core-shell type rubber particles (D), coupling agent (E), and curing accelerator (F) (hereinafter referred to as "other components (G)"). Examples of other components (G) include curable compounds other than epoxy resin (A), thermoplastic resins such as polyethylene resin, polyester resin, polyurethane resin, and polyamide resin, ion trapping agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants, reactive diluents, elastomers, solvents, etc. Other components (G) may be used individually or in combination of two or more.

[0080] The content of other components (G) relative to the above 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 preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less. Also, for example, it may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more.

[0081] The solvent content relative to the epoxy resin composition (100% by mass) is preferably, for example, 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less. It is also, for example, 0.001% by mass or more.

[0082] The epoxy resin composition described above may or may not contain a styrene-butadiene compound or a PMMA-PnBA block polymer. When the epoxy resin composition contains a styrene-butadiene compound or a PMMA-PnBA block polymer, the coefficient of thermal expansion does not increase easily even at high temperatures, but delamination and cracking tend to occur more easily. Therefore, from the viewpoint of reducing the occurrence of delamination and cracking, it is preferable that the epoxy resin composition does not contain a styrene-butadiene compound or a PMMA-PnBA block polymer. The PMMA-PnBA block polymer is a copolymer of PMMA (polymethyl methacrylate) and PnBA (poly-n-butyl acrylate).

[0083] The epoxy resin composition described above may or may not contain phosphoric acid or polyester phosphate. When the epoxy resin composition contains phosphoric acid or polyester phosphate, the dispersibility of the components in the composition improves, but the strong hydrophilicity of the phosphoric acid group tends to increase the hygroscopicity of the composition and its cured product. Therefore, from the viewpoint of reducing hygroscopicity, it is preferable that the epoxy resin composition does not contain phosphoric acid or polyester phosphate.

[0084] The viscosity of the epoxy resin composition at 25°C (at 50 rpm) is not particularly limited, but is preferably 1.0 Pa·s or higher, more preferably 3.0 Pa·s or higher, even more preferably 6.0 Pa·s or higher, and particularly preferably 9.0 Pa·s or higher. Alternatively, it is preferably 100 Pa·s or lower, more preferably 90 Pa·s or lower, even more preferably 80 Pa·s or lower, even more preferably 70 Pa·s or lower, even more preferably 60 Pa·s or lower, and particularly preferably 50 Pa·s or lower. When the viscosity is within the above range, the epoxy resin composition tends to have good injectability. The viscosity can be measured using a Brookfield HBDV-1 viscometer (using a spindle SC4-14) with the epoxy resin composition at a liquid temperature of 25°C and rotated at 50 rpm for 1 minute, as shown in the examples described later.

[0085] The viscosity of the epoxy resin composition at 25°C (at 10 rpm) is not particularly limited, but is preferably 1.0 Pa·s or higher, more preferably 2.0 Pa·s or higher, even more preferably 3.0 Pa·s or higher, and particularly preferably 5.0 Pa·s or higher. Alternatively, it is preferably 60 Pa·s or lower, more preferably 40 Pa·s or lower, even more preferably 30 Pa·s or lower, even more preferably 20 Pa·s or lower, and particularly preferably 15 Pa·s or lower. When the viscosity is within the above range, the epoxy resin composition tends to have good injectability. The viscosity can be measured using a Brookfield HBDV-1 viscometer (using a spindle SC4-14) with the epoxy resin composition at a liquid temperature of 25°C and rotated at 10 rpm for 1 minute, as shown in the examples described later.

[0086] The viscosity of the epoxy resin composition at 25°C (5 rpm) is not particularly limited, but is preferably 1.0 Pa·s or higher, more preferably 2.0 Pa·s or higher, even more preferably 3.0 Pa·s or higher, and particularly preferably 5.0 Pa·s or higher. Alternatively, it is preferably 60 Pa·s or lower, more preferably 40 Pa·s or lower, even more preferably 30 Pa·s or lower, even more preferably 20 Pa·s or lower, and particularly preferably 15 Pa·s or lower. When the viscosity is within the above range, the epoxy resin composition tends to have good injectability. The viscosity can be measured using a Brookfield HBDV-1 viscometer (using a spindle SC4-14) with the epoxy resin composition at a liquid temperature of 25°C and rotated at 5 rpm for 1 minute, as shown in the examples described later.

[0087] (Method for manufacturing epoxy resin composition) The epoxy resin composition described above can be prepared by known and conventional methods. For example, the epoxy resin composition can be obtained by simultaneously or separately introducing epoxy resin (A), curing agent (B), inorganic filler (C), and at least one selected from the group consisting of core-shell type rubber particles (D), coupling agent (E), curing accelerator (F), and other components (G) into a suitable mixer and stirring and mixing while melting by heating as needed. If the epoxy resin (A) is solid, it is preferable to liquefy or fluidize it 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) may be heated and mixed to uniformly disperse the inorganic filler (C) in the epoxy resin (A), then cooled as needed, and further mixing in components such as the curing agent (B) to prepare the epoxy resin composition.

[0088] The above-mentioned mixer is not particularly limited, but examples include a three-roll mill equipped with a stirring device and a heating device, a roll mill, a Leikai mill, a Henschel mixer, a tumbler, a self-rotating mill, a planetary mixer, etc. The mixing ratio of each component is appropriately set according to the content ratio of each component in the epoxy resin composition.

[0089] The above epoxy resin composition can be preferably used as a material (epoxy resin composition for semiconductor encapsulation) for encapsulating materials arranged on a substrate, such as semiconductor elements, wiring, and solder (solder bumps), in semiconductor devices. By using the above epoxy resin composition as an epoxy resin composition for semiconductor encapsulation, highly reliable semiconductor devices can be manufactured. Furthermore, the above epoxy resin composition can be preferably used as a material (epoxy resin composition for flip-chip semiconductor encapsulation) for encapsulating semiconductor elements, etc., arranged on a substrate in flip-chip type semiconductor devices. Specifically, by filling the gap between the semiconductor element, etc., and the substrate with the above epoxy resin composition and applying heat curing, the bumps present in the gap are encapsulated, and the semiconductor element and the substrate are fixed to each other as an encapsulant, thereby improving reliability and reducing the occurrence of bump connection failures.

[0090] The above-mentioned epoxy resin composition for semiconductor encapsulation can be used, for example, as an underfill such as capillary underfill, liquid mold underfill, secondary underfill, or pre-filled underfill, as well as a grab-top material and a liquid compression mold material. The above-mentioned epoxy resin composition is not limited to its use as an epoxy resin composition for semiconductor encapsulation as described above, and can be used, for example, as an adhesive for fixing, joining, or protecting components that constitute electronic components.

[0091] (Cured epoxy resin composition) A cured product is formed by curing the above epoxy resin composition. The curing method is not particularly limited, but for example, it can be carried out by heat treatment of the epoxy resin composition. The heat treatment temperature is not particularly limited, but for example, 60 to 200°C is preferred, and 80 to 180°C is more preferred. The heat treatment time is not particularly limited, but for example, 0.1 to 5 hours is preferred, and 0.5 to 3 hours is more preferred.

[0092] In the cross-section of the cured product (50 μm vertically × 2 cm horizontally), it is preferable that the number of hollow particles derived from the inorganic filler (C) is one or less. The number of hollow particles derived from the inorganic filler (C) in the cross-section of the cured product can be measured by observation using a scanning electron microscope (SEM) under specific conditions, as described in the examples below.

[0093] (Semiconductor device) The semiconductor device of the present invention comprises a substrate, a semiconductor element disposed on the substrate, and a cured product of the epoxy resin composition that encapsulates the semiconductor element. Preferably, the semiconductor device is a flip-chip type semiconductor device. A flip-chip type semiconductor device has a structure in which an electrode portion on the substrate and a semiconductor element are connected via bumps. In addition, in the semiconductor device, the gap between the semiconductor element and the substrate is sealed by the cured product (encapsulant) of the epoxy resin composition.

[0094] A semiconductor device can be manufactured by filling the gap between the substrate and the semiconductor element placed on the substrate with the epoxy resin composition (filling step), and then heating and curing the epoxy resin composition (sealing step). The method of filling the gap with the epoxy resin composition is not particularly limited, but for example, by heating the substrate to 50 to 120°C and applying the epoxy resin composition to one end of the substrate or semiconductor element, the epoxy resin composition is filled into the gap between the substrate and the semiconductor element by capillary action. After filling the gap with the epoxy resin composition, the gap is sealed by heating the substrate at a predetermined temperature for a predetermined time, specifically at the temperature and time described in the heat treatment for forming the cured product. [Examples]

[0095] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0096] The epoxy resin compositions of the examples and comparative examples were prepared by appropriately selecting and mixing components such as epoxy resin (A) to achieve the mixing ratios shown in Table 1. The numerical values ​​for each composition in Table 1 represent parts by mass.

[0097] The following is a description of each component in Table 1. • Epoxy resin (A) YDF-8170 (Product Name): Bisphenol F type epoxy resin, epoxy equivalent weight 158 ​​g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. jER 630 (Product Name): Aminophenol-type epoxy resin (aromatic amine-type trifunctional epoxy resin), epoxy equivalent weight 98 g / eq, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation. HP-4032D (Product Name): Naphthalene-type epoxy resin, epoxy equivalent weight 140 g / eq, liquid at 25°C, manufactured by DIC Corporation. ZX-1658GS (Product Name): 1,4-Glycidylcyclohexane, epoxy equivalent 135 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. • Hardener (B) HD AA: Product name is "KAYAHARD AA", amine-based curing agent, 4,4'-diamino-3,3'-diethyldiphenylmethane, active hydrogen equivalent is 63.5 g / eq, manufactured by Nippon Kayaku Co., Ltd. EH-105L: Product name is ADEKA EH-105L, modified aromatic amine-based curing agent, active hydrogen equivalent is 61g / eq, manufactured by ADEKA Corporation. EtaCure 100 (product name): Amine-based curing agent, active hydrogen equivalent 44.6 g / eq, diethyltoluenediamine, manufactured by Albemar Co., Ltd. ·Inorganic filler (C) YA010A-JGP (Product Name): A masterbatch of silica surface-treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and bisphenol F type epoxy resin. The silica content is 30% by mass, the average particle size is 10 nm, manufactured by Admatex Co., Ltd. The values ​​in Table 1 represent the mass of silica, and the mass of bisphenol F type epoxy resin is added to YDF-8170. SE203G-SEJ (Product Name): Silica surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.5 μm, top cut diameter 3 μm, manufactured by Admatex Co., Ltd., inorganic filler obtained by combustion method. SE101G-SEO (Product Name): Silica surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.3 μm, top cut diameter 3 μm, manufactured by Admatex Co., Ltd., inorganic filler obtained by combustion method. SE2050-SEJ (Product Name): Silica surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.5 μm, top cut diameter 5 μm, manufactured by Admatex Co., Ltd., inorganic filler obtained by combustion method. SE1050-SEO (Product Name): Silica surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.3 μm, top cut diameter 5 μm, manufactured by Admatex Co., Ltd., inorganic filler obtained by combustion method. • Core-shell type rubber particles (D) MX-965 (Product Name): Core-shell type silicone rubber particles, manufactured by Kaneka Corporation. • Coupling agent (E) KBM-403 (Product Name): 3-Glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. • Curing accelerator (F) CG1400 (Product Name): Dicyandiamide, curing accelerator, manufactured by Air Products & Chemicals Co., Ltd. Other ingredients (G) TPP (Product Name): Triphenylphosphine, Thickening Inhibitor, Manufactured by Hokko Chemical Industry Co., Ltd. Black 4: Product name is "Special Black 4 powder", carbon black, manufactured by Orion Engineered Carbon. KF-6013: Polyether-modified silicone, leveling agent, manufactured by Shin-Etsu Chemical Co., Ltd.

[0098] (Evaluation 1: Measurement of viscosity at 25°C) The viscosity (Pa·s) of the epoxy resin compositions of the examples and comparative examples at 25°C was measured using a Brookfield HBDV-1 viscometer (using a SC4-14 spindle) with the epoxy resin composition at a liquid temperature of 25°C, and the viscosity was measured when the mixture was rotated at 50 rpm, 10 rpm, or 5 rpm for 1 minute. The results are listed in Table 1 under "Viscosity at 25°C (Pa·s)" for "50 rpm", "10 rpm", and "5 rpm".

[0099] (Evaluation 2: Gap filling test) • Preparation of test specimens A test specimen was obtained by attaching a glass plate to a resin substrate (FR4) with tape, resulting in a gap between the FR4 and the glass plate. The gap had a height of 50 μm, a width of 1 cm, and a distance of 2 cm.

[0100] • Testing and evaluation The above test specimen was placed on a hot plate set to 110°C, and approximately 0.2 g of the epoxy resin composition of the example and comparative example was applied to one end (sample application area). The time taken until the filling distance reached 2 cm was measured.

[0101] The gap filling test will be explained using Figure 1. In Figure 1, 1 represents the test specimen. 2 is a glass plate, and 2' is a resin substrate (FR4). 3 is a tape. 4 is the gap. 5 is the evaluation sample. (a) is a plan view of test specimen 1, with the longitudinal direction of test specimen 1 as vertical and the transverse direction as transverse. (b) is a side view of test specimen 1 from the longitudinal direction. (c) is a side view of test specimen 1 from the transverse direction. The glass plate 2 is laminated with the resin substrate 2' via tape 3. As shown in (b), the edge of the glass plate 2 is the coated area (sample coated area) of the evaluation sample 5. The gap 4 is a space enclosed by the glass plate 2 on its top surface, the resin substrate 2' on its bottom surface, and two tapes 3 on its sides. In gap 4, the distance between the glass plate 2 and the resin substrate 2' (gap height) is 50 μm, and the distance between the two tapes 3 (gap width) is 1 cm. The longitudinal distance of gap 4 (gap distance) is 2 cm. Test specimen 1 is placed on a hot plate (not shown), and evaluation sample 5 is applied to the sample application area. The applied evaluation sample 5 moves downwards towards (a) through gap 4 by capillary action. The time it takes for evaluation sample 5 to reach the edge of the glass slide 2' is measured, and the result is recorded in "Injectability (seconds)" in Table 1. If evaluation sample 5 does not reach the edge after 1000 seconds or more, the evaluation is stopped immediately, and the result is indicated as "Stop" in Table 1.

[0102] (Evaluation 3: Observation of hollow particles in the cross-section of the hardened material) The test specimens filled with the epoxy resin compositions of the examples and comparative examples used in the gap-filling test of Evaluation 2 were cured at 165°C for 120 minutes. The cross-section of the resulting cured material was observed using a scanning electron microscope (SEM) SU3800 (manufactured by Hitachi High-Tech Corporation). The pressurized voltage was 5.00kV, the spot intensity was 50, the working distance (WD) was 10mm, and the observation magnification was 1000x, and the number of hollow particles in the cross-section was measured. Hollow particles were defined as particles with a particle size of 0.1 to 10 μm and having a hollow portion of 20% or more in terms of area inside the particle. These are called hollow particles derived from the inorganic filler (C). The observed cross-section of the cured material was obtained by cutting the cured material (1 cm long × 2 cm wide × 50 μm thick when viewed from above) in the longitudinal direction, and the size in plan view was 50 μm long × 2 cm wide. Figures 3 and 4 are partial cross-sectional images of the cured material in Examples 1 and 4, respectively. The cross-sections used for observation were prepared by cutting the hardened material at 20 arbitrary points. The number of hollow particles present in each cross-section was counted, and the average of the obtained values ​​was recorded in "Number of Hollow Particles" in Table 1.

[0103] [Table 1] [Explanation of Symbols]

[0104] 1 Test specimen 2 glass plates 2' Resin base material 3 tapes 4 gaps 5 Evaluation Samples 11 Underfill 12 Bump 13 Hollow inorganic filler

Claims

1. Epoxy resin (A), Hardener (B), Inorganic filler (C), and An epoxy resin composition containing a curing accelerator (F), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The curing accelerator (F) includes at least one selected from the group consisting of imidazole-based curing accelerators (F1), tertiary amine-based curing accelerators (F2), phosphorus-based curing accelerators (F3), and dicyandiamide. The content of the curing agent (B) relative to the epoxy resin composition (100% by mass) is 3% by mass or more. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. Silica-free obtained by the sol-gel method, The viscosity at 25°C (10 rpm) is 60 Pa·s or less. An epoxy resin composition for underfill.

2. Epoxy resin (A), Hardener (B), Inorganic filler (C), and An epoxy resin composition containing a curing accelerator (F), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The curing accelerator (F) includes at least one selected from the group consisting of imidazole-based curing accelerators (F1), tertiary amine-based curing accelerators (F2), phosphorus-based curing accelerators (F3), and dicyandiamide. The content of the curing agent (B) relative to the epoxy resin composition (100% by mass) is 3% by mass or more. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. Silica-free obtained by the sol-gel method, An epoxy resin composition for underfill.

3. Epoxy resin (A), Hardener (B), and An epoxy resin composition comprising an inorganic filler (C), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The content of the curing agent (B) relative to the epoxy resin composition (100% by mass) is 3% by mass or more. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. Silica-free obtained by the sol-gel method, The viscosity at 25°C (10 rpm) is 60 Pa·s or less. An epoxy resin composition for underfill.

4. Epoxy resin (A), Hardener (B), and An epoxy resin composition containing an inorganic filler (C), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The content of the curing agent (B) relative to the epoxy resin composition (100% by mass) is 3% by mass or more. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. Silica-free obtained by the sol-gel method, An epoxy resin composition for underfill.

5. Epoxy resin (A), Hardener (B), Inorganic filler (C), and An epoxy resin composition containing a curing accelerator (F), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. The curing accelerator (F) includes at least one selected from the group consisting of imidazole-based curing accelerators (F1), tertiary amine-based curing accelerators (F2), phosphorus-based curing accelerators (F3), and dicyandiamide. Silica-free obtained by the sol-gel method, The viscosity at 25°C (10 rpm) is 60 Pa·s or less. An epoxy resin composition for underfill.

6. Epoxy resin (A), Hardener (B), Inorganic filler (C), and An epoxy resin composition containing a curing accelerator (F), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. The curing accelerator (F) includes at least one selected from the group consisting of imidazole-based curing accelerators (F1), tertiary amine-based curing accelerators (F2), phosphorus-based curing accelerators (F3), and dicyandiamide. Silica-free obtained by the sol-gel method, An epoxy resin composition for underfill.

7. Epoxy resin (A), Hardener (B), and An epoxy resin composition containing an inorganic filler (C), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. Silica-free obtained by the sol-gel method, The viscosity at 25°C (10 rpm) is 60 Pa·s or less. An epoxy resin composition for underfill.

8. Epoxy resin (A), Hardener (B), and An epoxy resin composition containing an inorganic filler (C), The curing agent (B) contains an aromatic amine, The inorganic filler (C) includes silica obtained by combustion, which may have a surface treatment, and has a top cut diameter of 3.0 μm or less. The inorganic filler (C) (100% by mass) contains 60% by mass or more of silica obtained by combustion, with a top cut diameter of 3.0 μm or less, and which may have a treated surface. Silica-free obtained by the sol-gel method, An epoxy resin composition for underfill.

9. The epoxy resin composition according to any one of claims 1 to 8, wherein the number of hollow particles derived from the inorganic filler (C) in the cross-section of the cured product (50 μm vertically × 2 cm horizontally) is one or less.

10. An epoxy resin composition according to any one of claims 1 to 8, which does not contain styrene-butadiene compounds and PMMA-PnBA block polymers.

11. An epoxy resin composition according to any one of claims 1 to 8, which does not contain phosphoric acid or does not contain phosphate polyester.

12. The epoxy resin composition according to any one of claims 1 to 8, wherein the epoxy resin (A) does not contain a silicone resin having two or more epoxy groups in one molecule.

13. The epoxy resin composition according to any one of claims 1 to 8, wherein the inorganic filler (C) content is 30 to 80% by mass.

14. The epoxy resin composition according to any one of claims 1 to 8, wherein the inorganic filler (C) comprises an inorganic filler (C2) having an average particle size of 1 nm or more and less than 100 nm.

15. The epoxy resin composition according to any one of claims 1 to 8, wherein the epoxy resin (A) comprises at least one selected from bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and 1,4-glycidylcyclohexane.

16. The epoxy resin composition according to any one of claims 1 to 8, further comprising core-shell type rubber particles (D).

17. An epoxy resin composition according to any one of claims 1 to 8, for use in semiconductor encapsulation.

18. A cured product of the epoxy resin composition according to any one of claims 1 to 8.

19. circuit board and A semiconductor element disposed on the aforementioned substrate, A cured product according to claim 18 for sealing the semiconductor element, A semiconductor device equipped with a semiconductor device.

20. A step of filling the gap between the substrate and the semiconductor element disposed on the substrate with the epoxy resin composition according to any one of claims 1 to 8, A step of heating and curing the epoxy resin composition, A method for manufacturing a semiconductor device containing [a specific component].

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