Epoxy resin composition, cured product, semiconductor device, and method for producing semiconductor device

Abstract

Provided is an epoxy resin composition which gives a cured product having good adhesion strength and a sufficiently low coefficient of thermal expansion. Also provided are: a cured product formed from the epoxy resin composition; a semiconductor device including the cured product; and a method for producing the semiconductor device.　The epoxy resin composition comprises an epoxy resin (A), an aromatic amine compound (B), and an inorganic filler (C), the composition comprising, as the inorganic filler (C), zeolite (C1) having a coefficient of thermal expansion of -20 to -3 ppm / °C.

Description

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

[0001] This invention relates to epoxy resin compositions, cured products, semiconductor devices, and methods for manufacturing semiconductor devices.

[0002] Semiconductor devices are required to be high-performance, multi-functional, and power-efficient. Until now, the mainstream approach was SoC (System on a Chip), which integrates transistors and provides all functions on a single chip. However, this presented problems such as rising manufacturing costs and decreased yield due to the increasing size of the chips. In response to this, SiP (System in a Package) emerged, which manufactures functions (systems) on multiple chips and integrates them at high density.

[0003] In SiP (System-in-Package), a substrate called an interposer (e.g., a silicon interposer) is used. The interposer is placed on top of the package substrate, and multiple chips are arranged on top of it. Furthermore, a multilayer wiring circuit is formed on the upper side of the interposer and connected to the substrate below by TSVs (Through-Silicon Vias). Since no active elements such as transistors are formed on the interposer, it is easier to scale up compared to chips. Therefore, it has become common practice to enlarge the interposer and mount more chips. In addition, various interposer technologies are being considered for further scaling, such as interposers with silicon embedded in molded resin and interposers formed only of multilayer wiring layers. The chips and the interposer, and the interposer and the resin substrate are connected via bump electrodes.

[0004] When thermal loads such as temperature cycles are applied, stress is placed on the bump electrodes due to differences in the linear thermal expansion coefficients of each component, leading to defects such as cracks. To address this, sealing resin compositions such as liquid sealing material called underfill, or liquid molding material that seals the entire package, are used in the gaps between the chip and the interposer, and between the interposer and the resin substrate. These measures improve resistance to thermal loads (thermal cycle resistance) and package protection performance to protect the package from heat and external forces.

[0005] In recent years, as semiconductor devices have pursued further improvements in performance and functionality, semiconductor packages have become larger. This increase in package size leads to increased thermal stress due to differences in thermal expansion coefficients between components. Therefore, to improve the thermal cycling resistance of semiconductor devices, it is necessary to reduce the thermal expansion coefficient of the cured resin material used for sealing. Furthermore, from the viewpoint of reliability (e.g., low peelability and moisture resistance), the adhesive strength of the cured material to the semiconductor package is also required. For example, an underfill material using silica as a filler is known for its purpose of reducing the thermal expansion coefficient of the cured material (Patent Document 1). Also known is an underfill material containing an epoxy resin, a curing agent, and silica as an inorganic filler, wherein the epoxy resin is an aliphatic epoxy resin (neopentyl glycol diglycidyl ether) (Patent Document 2). Furthermore, an underfill material containing a specific epoxy resin, a curing agent, and silica as an inorganic filler is known (Patent Document 3). Finally, a composition containing an epoxy resin, a zeolite, an acid anhydride-based curing agent, and a dispersant having at least one of the functional groups of an amino group and an amine salt is known (Patent Document 4). Furthermore, a liquid composition containing epoxy resin, a specific zeolite, and an acid anhydride-based curing agent is known (Patent Document 5).

[0006] Japanese Patent Publication No. 2018-123340, Japanese Patent Publication No. 2019-129275, Japanese Patent Publication No. 2019-083225, Japanese Patent Publication No. 2022-074145, International Publication No. 2023 / 210791

[0007] However, the cured products of the underfill materials described in Patent Documents 1 to 3 exhibited high coefficients of thermal expansion and failed to solve the problems of the increasingly large semiconductor packages of today. Furthermore, when the type of inorganic filler was changed in order to reduce the coefficient of thermal expansion of the cured product, the adhesive strength also tended to decrease, and no resin composition that satisfied both of these properties and provided a cured product had been found. In addition, as described in Patent Documents 4 and 5, although the coefficient of thermal expansion of the cured product decreases when zeolite is used instead of silica as the inorganic filler, compositions containing zeolite tend to become more viscous, and it is known that the injectability when used as an underfill material decreases. For this reason, when trying to obtain an underfill material with a low viscosity (good injectability) while lowering the coefficient of thermal expansion of the cured product, zeolite was not used instead of silica as the inorganic filler.

[0008] Furthermore, in the compositions described in Patent Documents 4 and 5, acid anhydride-based curing agents are used as curing agents in order to obtain the excellent injectability required for underfill materials. However, these compositions had the problem of not being able to obtain sufficient adhesive strength. It also became clear that the fracture toughness of the cured products was low (see Comparative Example 2 of this application).

[0009] Therefore, an object of the present invention is to provide an epoxy resin composition that yields a cured product with good adhesive strength and a sufficiently low coefficient of thermal expansion. 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.

[0010] 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.

[0011] In other words, the present invention provides an epoxy resin composition comprising an epoxy resin (A), an aromatic amine compound (B), and an inorganic filler (C), wherein the inorganic filler (C) comprises a zeolite (C1) having a thermal expansion coefficient of -20 to -3 ppm / °C.

[0012] In the epoxy resin composition described above, the epoxy resin (A) preferably contains at least one selected from the group consisting of bisphenol-type epoxy resins, aminophenol-type epoxy resins, naphthalene-type epoxy resins, and cyclohexane-type epoxy resins.

[0013] The epoxy resin composition described above preferably further contains silica (C2) as the inorganic filler (C).

[0014] The content of zeolite (C1) relative to 100% by mass of the inorganic filler (C) is preferably 30% by mass or more.

[0015] The sphericity of the zeolite (C1) is preferably 0.6 or more.

[0016] The epoxy resin composition described above is preferably for semiconductor encapsulation.

[0017] The epoxy resin composition described above is preferably an underfill material.

[0018] The present invention also provides a cured product of the epoxy resin composition described above.

[0019] The present invention also provides a semiconductor device including: a substrate; a semiconductor element disposed on the substrate; and the cured product described above that encapsulates the semiconductor element.

[0020] The present invention also provides a method for manufacturing a semiconductor device, including the steps of: filling a gap between a substrate and a semiconductor element disposed on the substrate with the epoxy resin composition described above; and heating and curing the epoxy resin composition described above.

[0021] The epoxy resin composition of the present invention has the characteristics that a cured product thereof has good adhesive strength and a sufficiently low coefficient of thermal expansion. Further, a semiconductor device including a cured product of the epoxy resin composition described above exhibits high thermal cycle resistance.

[0022] (Epoxy resin composition) The epoxy resin composition of the present invention comprises an epoxy resin (A), an aromatic amine compound (B), and an inorganic filler (C), and is characterized in that it contains, as the inorganic filler (C), a zeolite (C1) having a thermal expansion coefficient of -20 to -3 ppm / °C.

[0023] • Epoxy resin (A) By including the epoxy resin (A) in the above epoxy resin composition, a cured product having high electrical insulation properties can be formed. The number of epoxy groups contained in the epoxy resin (A) is not particularly limited as long as it is 1 or more, but it is preferably 2 or more (that is, the epoxy resin is a polyfunctional type epoxy resin). One type of the epoxy resin (A) may be used alone, or two or more types may be used in combination.

[0024] The epoxy resin (A) may be liquid or solid at ordinary temperature (25°C), but is preferably liquid from the viewpoint of the viscosity and injectability of the epoxy resin composition. Even a solid epoxy resin can be preferably used when it exhibits liquid state as a mixture when used in combination with a liquid epoxy resin. The term "injectability" refers to the ease of injecting the epoxy resin composition into the gap between a substrate and a semiconductor element, and can also be rephrased as ease of filling.

[0025] 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, Examples include naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, 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, 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.

[0026] From the viewpoint of adhesive strength and thermal expansion coefficient of the cured product, the epoxy resin composition described above preferably contains at least one selected from bisphenol-type epoxy resins (e.g., bisphenol A-type epoxy resin, bisphenol F-type epoxy resin), aminophenol-type epoxy resin, naphthalene-type epoxy resin, and cyclohexane-type epoxy resin (e.g., 1,4-glycidylcyclohexane) as the epoxy resin (A). Furthermore, from the viewpoint of fracture toughness of the cured product, it is more preferable to contain at least one selected from bisphenol F-type epoxy resin, naphthalene-type epoxy resin, and 1,4-glycidylcyclohexane.

[0027] 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 "jER828E" from Mitsubishi Chemical Corporation. L (all are bisphenol A type epoxy resins), jER806, jER807 (both are bisphenol F type epoxy resins), jER152 (phenol novolac type epoxy resin), jER630, jER630LSD (both 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 epoxy) manufactured by Asahi Kasei Corporation. Examples include: ol-type epoxy resins, "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins); "DER852" and "DER858" from Dow Chemical Ltd. (both oxazolidone ring-containing epoxy resins); "FAE-2500" and "EPPN-501HY" from Nippon Kayaku Co., Ltd. (both trisphenolmethane-type epoxy resins), "RE410S" (bisphenol A-type epoxy resin); and "Celoxide 2021P" from Daicel Corporation (alicyclic epoxy resin).

[0028] Specific examples of solid epoxy resins include "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" manufactured by 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) manufactured by Mitsubishi Chemical Corporation.

[0029] 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.

[0030] The content of epoxy resin (A) in the above epoxy resin composition (100% by mass) 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, and particularly preferably 20% by mass or more. Alternatively, it is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 37% 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 cured product of the epoxy resin composition tends to have excellent adhesive strength and thermal expansion coefficient. Furthermore, the epoxy resin composition tends to have excellent injectability.

[0031] In the epoxy resin composition described above, a high content of bisphenol-type epoxy resin is preferable from the viewpoint of fracture toughness of the cured product. The content of bisphenol-type epoxy resin relative to epoxy resin (A) (100% by mass) in the epoxy resin composition described above is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 65% ​​by mass or more, even more preferably 75% by mass or more, and particularly preferably 85% by mass or more.

[0032] In the epoxy resin composition described above, from the viewpoint of fracture toughness of the cured product, it is preferable that the content of aminophenol-type epoxy resin be relatively low. The content of aminophenol-type epoxy resin relative to epoxy resin (A) (100% by mass) in the epoxy resin composition described above is not particularly limited, but is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0033] In the epoxy resin composition described above, from the viewpoint of heat resistance and mechanical strength, it is preferable that the content of aliphatic epoxy resin (especially neopentyl glycol diglycidyl ether) is not high. The content of aliphatic epoxy resin relative to epoxy resin (A) (100% by mass) in the epoxy resin composition described above is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

[0034] • Aromatic amine compound (B) Aromatic amine compound (B) is a curing agent for epoxy resins, and when incorporated into the epoxy resin composition described above, it can improve the adhesive strength and fracture toughness of the cured product.

[0035] The aromatic amine compound (B) may be liquid or solid at room temperature (25°C), but it is preferable that it be liquid from the viewpoint of viscosity and injectability of the epoxy resin composition. Even if the aromatic amine compound (B) is solid, it can preferably be used if it becomes liquid as a mixture when used in combination with a liquid epoxy resin.

[0036] Examples of aromatic amine compounds (B) include 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-methylenebis(2-ethylaniline), diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. Aromatic amine compounds (B) can be used individually or in combination of two or more.

[0037] The active hydrogen equivalent of aromatic amine compound (B) is not particularly limited, but is preferably 10 to 300 g / eq, more preferably 15 to 200 g / eq, even more preferably 20 to 150 g / eq, even more preferably 25 to 100 g / eq, and most preferably 30 to 80 g / eq.

[0038] The content of aromatic amine compound (B) in the epoxy resin composition described above is not particularly limited, but it is preferably an amount such that the stoichiometric equivalent ratio (active hydrogen equivalent / epoxy group equivalent) with epoxy resin (A) is, for example, 0.4 to 1.6, more preferably 0.5 to 1.4, even more preferably 0.6 to 1.2, and particularly preferably 0.7 to 1.0.

[0039] The content of aromatic amine compound (B) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 4% by mass or more, more preferably 6% by mass or more, even more preferably 8% by mass or more, and particularly preferably 9% by mass or more. Alternatively, it is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 16% by mass or less, and particularly preferably 14% by mass or less. When the content of aromatic amine compound (B) is within the above range, the adhesive strength and fracture toughness of the cured product tend to be further improved.

[0040] The content of aromatic amine compound (B) relative to epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 16% by mass or more, more preferably 20% by mass or more, even more preferably 24% by mass or more, even more preferably 28% by mass or more, even more preferably 32% by mass or more, and particularly preferably 34% by mass or more. Alternatively, it is preferably 100% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the content of aromatic amine compound (B) is within the above range, the adhesive strength and fracture toughness of the cured product tend to be further improved.

[0041] • 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.

[0042] Examples of inorganic fillers (C) include silica (silicon dioxide), zeolite, 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 materials with treated surfaces (surface-treated materials). Inorganic fillers (C) can be used individually or in combination of two or more types.

[0043] 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. One of the coupling agents can be used alone for surface treatment of the inorganic filler (C), or two or more can be used in combination.

[0044] 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, from the viewpoint of achieving a high filling capacity, the shape of the inorganic filler (C) is preferably spherical.

[0045] 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 8 μm, even more preferably 10 nm to 6 μm, and particularly preferably 30 nm to 5 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: Mastersizer 3000, manufactured by Malvern Panalogical).

[0046] The epoxy resin composition described above includes a zeolite (C1) as an inorganic filler (C), having a thermal expansion coefficient of -20 to -3 ppm / °C. The zeolite can be described as a microporous crystalline aluminosilicate. The surface of the zeolite (C1) may be treated with a coupling agent having a functional group such as an epoxy group, a (meth)acryloyl group, or an amino group (especially 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. One of the coupling agents can be used alone for surface treatment of the zeolite (C1), or two or more can be used in combination.

[0047] The epoxy resin composition described above contains zeolite (C1), which has a low coefficient of thermal expansion, as an inorganic filler, thereby reducing the coefficient of thermal expansion of the cured product. Furthermore, compared to silica (silica filler), which is commonly used as an inorganic filler, zeolite has a lower modulus of elasticity and a lower specific gravity. Therefore, using zeolite (C1) can be expected to reduce the elasticity of the cured product. This reduced elasticity improves resistance to impact and bending, and tends to reduce crack formation. Additionally, because zeolite (C1) has a low specific gravity, the phenomenon of zeolite (C1) settling due to the difference in specific gravity with the resin can be reduced, which is expected to improve the uniformity of the cured product. The specific gravity of silica (silica filler), which is commonly used as an inorganic filler, is 2.2 g / cm³. ３ It is approximately as follows. The specific gravity of zeolite (C1) is, for example, 1.0 g / cm³. ３ The above is preferable, and more preferably 1.3 g / cm³. ３ More preferably 1.5 g / cm³ ３ That's all. Also, for example, 2.2 g / cm³ ３ Preferably less than 2.15 g / cm³, and more preferably 2.15 g / cm³. ３ Less than 2.1 g / cm³, more preferably 2.1 g / cm³ ３ Less than 2.0 g / cm³, particularly preferably 2.0 g / cm³ ３ It is less than.

[0048] The thermal expansion coefficient of zeolite (C1) is not particularly limited as long as it is between -20 and -3 ppm / °C, but is preferably -18 ppm / °C or higher, more preferably -16 ppm / °C or higher, even more preferably -14 ppm / °C or higher, and particularly preferably -12 ppm / °C or higher. It is also preferably -4 ppm / °C or lower, more preferably -5 ppm / °C or lower, even more preferably -6 ppm / °C or lower, and particularly preferably -7 ppm / °C or lower. When the thermal expansion coefficient of zeolite (C1) is within the above range, the adhesive strength of the cured product tends to be further improved and the thermal expansion coefficient tends to be further reduced.

[0049] The sphericity of zeolite (C1) is not particularly limited, but for example, it is preferably 0.6 or more, more preferably 0.65 or more, still more preferably 0.7 or more, still more preferably 0.75 or more, and particularly preferably 0.78 or more. In addition, the upper limit of sphericity is not particularly limited, and it only needs to be 1 or less. The sphericity of a cube, which is common in conventional zeolites, is 0.58. In the present specification, "sphericity" is defined as "the ratio of the minimum diameter to the maximum diameter of a particle (= minimum diameter / maximum diameter)". The maximum diameter and minimum diameter of zeolite can each be determined by observation with a scanning electron microscope (SEM).

[0050] The circularity of zeolite (C1) is not particularly limited, but for example, it is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 0.85 or more, and particularly preferably 0.9 or more. In addition, the upper limit of circularity is not particularly limited, and it only needs to be 1 or less. The circularity of a cube, which is common in conventional zeolites, is 0.785. In the present specification, "circularity" is defined as "4 × π × area / (circumference) ２ ". The area and circumference can each be determined by observation with a scanning electron microscope (SEM).

[0051] The epoxy resin composition of the present invention may or may not contain silica as the inorganic filler (C). Silica may have a surface-treated structure. Silica and its surface-treated product are collectively referred to as silica (C2). That is, the epoxy resin composition may or may not contain silica (C2) as the inorganic filler (C). The coefficient of thermal expansion of silica (C2) is generally about 0.6 ppm / °C.

[0052] The content of the inorganic filler (C) in the 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, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more. Alternatively, it is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less. When the content of the inorganic filler (C) is within the above range, the epoxy resin composition tends to have excellent injectability.

[0053] When the above epoxy resin composition is used as an underfill material, the content of the inorganic filler (C) relative to the epoxy resin composition (100% by mass) is particularly preferably 50 to 70% by mass. Because the inorganic filler (C) content is within this range, the epoxy resin composition exhibits excellent injectability, and the adhesive strength of the cured product tends to be further improved, and the coefficient of thermal expansion tends to be further reduced, making it an excellent underfill material.

[0054] The content of zeolite (C1) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even 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. Also, is preferably 75% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. When the zeolite (C1) content is within the above range, the adhesive strength of the cured product tends to be further improved and the coefficient of thermal expansion tends to be further reduced.

[0055] The silica (C2) content relative to 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 5% by mass or more, and particularly preferably 10% by mass or more. Also, is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0056] 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, and particularly preferably 140% by mass or more. Also, is preferably 400% by mass or less, more preferably 360% by mass or less, even more preferably 320% by mass or less, even more preferably 280% by mass or less, and particularly preferably 240% 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.

[0057] The content of zeolite (C1) relative to 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 25% by mass or more, and particularly preferably 40% by mass or more. Also, is preferably 320% by mass or less, more preferably 280% by mass or less, even more preferably 240% by mass or less, even more preferably 200% by mass or less, and particularly preferably 160% by mass or less. When the zeolite (C1) content is within the above range, the adhesive strength of the cured product tends to be further improved and the coefficient of thermal expansion tends to be further reduced.

[0058] The silica (C2) content relative to the epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 4% by mass or more, more preferably 8% by mass or more, even more preferably 12% by mass or more, even more preferably 16% by mass or more, even more preferably 25% by mass or more, even more preferably 35% by mass or more, and particularly preferably 45% by mass or more. Also, is preferably 320% by mass or less, more preferably 240% by mass or less, even more preferably 200% by mass or less, even more preferably 160% by mass or less, and particularly preferably 120% by mass or less.

[0059] The content of zeolite (C1) relative to the inorganic filler (C) (100% by mass) in the epoxy resin composition described above is not particularly limited, but is preferably 4% by mass or more, more preferably 8% by mass or more, even more preferably 16% by mass or more, even more preferably 24% by mass or more, and particularly preferably 30% by mass or more. Also, is not particularly limited as long as it is 100% by mass or less, but is preferably 90% by mass or less, even more preferably 80% by mass or less, and particularly preferably 70% by mass or less. When the zeolite (C1) content is within the above range, the adhesive strength of the cured product tends to be further improved and the coefficient of thermal expansion tends to be further reduced.

[0060] • Curing accelerator (D) The epoxy resin composition described above may contain a curing accelerator (D). The curing accelerator (D) is not particularly limited as long as it is a curing accelerator for epoxy resins, but examples include imidazole-based curing accelerators such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Specific examples of the curing accelerator (D) include 2-phenyl-4-methylimidazole (product name: 2P4MZ), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product name: 2MZA), and disindiamide, all manufactured by Shikoku Chemicals, Inc. In addition, encapsulated imidazoles, such as microencapsulated imidazoles or epoxy adduct-type imidazoles, may be used. Examples include HX3941HP, HXA3942HP, HXA3922HP, HXA3792, HX3748, HX3721, HX3722, HX3088, HX3741, HX3742, HX3613 (all manufactured by Asahi Kasei Chemicals Corporation), PN-23J, PN-40J, PN-50 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and FXR-1121 (manufactured by Fuji Kasei Kogyo Co., Ltd.). The curing accelerator (D) can be used alone or in combination of two or more types.

[0061] The content of the curing accelerator (D) in the 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.

[0062] • Coupling agent (E) The epoxy resin composition may contain a coupling agent (E). Examples of the coupling agent (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.

[0063] Examples of the silane coupling agents mentioned above include 3-isocyanatetopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

[0064] The content of the coupling agent (E) 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 0.15% by mass or more, and particularly preferably 0.2% 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.

[0065] Other Components (F) The epoxy resin composition described above may contain components other than epoxy resin (A), aromatic amine compound (B), inorganic filler (C), curing accelerator (D), and coupling agent (E) (hereinafter referred to as "other components (F)"). Examples of other components (F) include curable compounds other than epoxy resin (A), thermoplastic resins such as polyethylene resin, polyester resin, polyurethane resin, and polyamide resin, curing agents other than aromatic amine compound (B), core-shell rubber particles, ion trapping agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants, reactive diluents, elastomers, solvents, etc. Other components (F) can be used individually or in combination of two or more.

[0066] Other curing agents besides the aromatic amine compound (B) mentioned above include phenol-based curing agents, acid anhydride-based curing agents, amine-based curing agents other than aromatic amine compounds, and imidazole-based curing agents.

[0067] The content of other components (F) 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 preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. Also, for example, it is 0.01% by mass or more.

[0068] From the viewpoint of reducing void formation in the cured product, the solvent content in the above 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. Alternatively, it may be, for example, 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more.

[0069] In the epoxy resin composition described above, from the viewpoint of reducing physical properties due to adsorption to the filler interface, it is preferable that the content of a dispersant having at least one of the functional groups of an amino group and an amine salt (see the dispersant described in Japanese Patent Application Publication No. 2022-074145) is not large. The content of the dispersant 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. Alternatively, it may be, for example, 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more.

[0070] The viscosity of the epoxy resin composition at 25°C is not particularly limited, but is preferably 2.5 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 500 Pa·s or lower, more preferably 400 Pa·s or lower, even more preferably 300 Pa·s or lower, even more preferably 200 Pa·s or lower, and particularly preferably 100 Pa·s or lower. When the viscosity is within the above range, the epoxy resin composition tends to have good injectability. If the viscosity of the epoxy resin composition at 25°C exceeds 200 Pa·s, it can be measured using a Brookfield HBDV-1 viscometer (using a spindle SC4-14) and the epoxy resin composition is rotated at 20 rpm for 1 minute with a liquid temperature of 25°C. Furthermore, if the viscosity is 200 Pa·s or less, as described in the examples below, it 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. If the viscosity of the epoxy resin composition at 25°C is lower than 20 Pa·s, it can be measured using a Brookfield RVDV-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.

[0071] In the epoxy resin composition described above, the glass transition temperature (Tg) of the cured product is not particularly limited, but is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 145°C or higher, and particularly preferably 150°C or higher. Alternatively, it is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower. When the glass transition temperature is within the above range, adhesion tends to improve, and reliability is also improved. The glass transition temperature can be determined by measuring the storage modulus (E') and loss modulus (E'') of the cured epoxy resin composition using a dynamic viscoelastic device, as described in the examples below, and taking the peak value of tanδ, which is the ratio of these two values, as the glass transition temperature (Tg). The above measurement may conform to the Japanese Industrial Standard JIS C6481. The cured product is obtained by curing at 180°C for 60 minutes.

[0072] (Method for producing 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 an epoxy resin (A), an aromatic amine compound (B), an inorganic filler (C), and at least one selected from the group consisting of a curing accelerator (D), a coupling agent (E), and other components (F) into a suitable mixer, and stirring and mixing them while melting them by heating as needed. If the epoxy resin (A) is solid, it is preferable to liquefy or fluidize it by heating and then mix it. If it is difficult to uniformly disperse the inorganic filler (C) in the epoxy resin composition, the epoxy resin (A) and the 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 an aromatic amine compound (B) to prepare the epoxy resin composition.

[0073] 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.

[0074] 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.

[0075] The above-mentioned epoxy resin composition for semiconductor encapsulation can be used, for example, as an underfill material such as a capillary underfill material, liquid mold underfill material, secondary underfill material, or pre-supplied underfill material, 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.

[0076] (Cured product of epoxy resin composition) A cured product is formed by curing the epoxy resin composition described above. 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.

[0077] In the cured product of the epoxy resin composition described above, the CTE (ppm / °C) below Tg is not particularly limited, but is preferably 15 to 31 ppm / °C, and more preferably 20 to 30 ppm / °C. In the cured product of the epoxy resin composition described above, the CTE (ppm / °C) above Tg is not particularly limited, but is preferably 40 to 120 ppm / °C, and more preferably 60 to 111 ppm / °C. The CTE below Tg and the CTE above Tg can be measured by the method described in the examples below.

[0078] In the cured product of the epoxy resin composition described above, the adhesive strength (initial adhesive strength) is not particularly limited, but is preferably 280 N or higher, more preferably 290 to 600 N, even more preferably 300 to 500 N, and particularly preferably 310 to 400 N. In the cured product of the epoxy resin composition described above, the adhesive strength after PCT is not particularly limited, but is preferably 180 N or higher, more preferably 200 to 500 N, even more preferably 220 to 400 N, and particularly preferably 230 to 320 N. The initial adhesive strength and the adhesive strength after PCT can be measured by the method described in the examples below.

[0079] In the cured product of the above epoxy resin composition, fracture toughness K ＩＣ (MPa・m １／２ ) is not particularly limited, but for example, 2.1 MPa·m １／２ Preferably, the pressure is 2.1 to 5 MPa·m or higher, and more preferably 2.1 to 5 MPa·m １／２ More preferably 2.2 to 4 MPa·m １／２ Furthermore, fracture toughness K ＩＣThis can be measured by the method described in the examples below.

[0080] (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. The flip-chip type semiconductor device has a structure in which an electrode portion on the substrate and the semiconductor element are connected via bumps. 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.

[0081] 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.

[0082] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0083] 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 component in Table 1 represent parts by mass.

[0084] The following describes 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. jER630 (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 (cyclohexane type epoxy resin), epoxy equivalent weight 135 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. • Aromatic amine compound (B) Kayahard A-A: 4,4'-methylenebis(2-ethylaniline), active hydrogen equivalent 63 g / eq, manufactured by Nippon Kayaku Co., Ltd. EtaCure 100 (product name): diethyltoluenediamine, active hydrogen equivalent 44.6 g / eq, manufactured by Albemarle Co., Ltd. Acid anhydride YH307 (product name): 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic acid anhydride, active hydrogen equivalent 234 g / eq, manufactured by Mitsubishi Chemical Corporation. Inorganic filler (C) Zeolite (C1) Zeolite A: Average particle size 1 μm, sphericity 0.89, roundness 0.91, CTE -8 ppm / °C, manufactured by Mitsubishi Chemical Corporation. Zeolite B: Average particle size 3.9 μm, sphericity 0.79, roundness 0.97, CTE -19 ppm / °C, manufactured by Mitsubishi Chemical Corporation. Zeolite C: Average particle size 3.4 μm, sphericity 0.90, roundness 0.96, CTE -19 ppm / °C, manufactured by Mitsubishi Chemical Corporation. Zeolite D manufactured by Mitsubishi Chemical Corporation: Average particle size 1.5 μm, sphericity 0.89, roundness 0.94, CTE -19 ppm / °C. Zeolite E manufactured by Mitsubishi Chemical Corporation: Zeolite A surface-treated with 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane content is 1.0% by mass relative to the total amount of zeolite, average particle size 1 μm, sphericity 0.89, roundness 0.91. Zeolite F: Zeolite A surface-treated with 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane content is 2.0% by mass relative to the total amount of zeolite, average particle size is 1 μm, sphericity is 0.89, roundness is 0.91. Silica (C2) SE2200-SEJ (product name): Silicon dioxide surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size is 0.6 μm, specific gravity is 2.2 g / cm. ３, Admatex Co., Ltd. YA010A-JGP (product name): Masterbatch of silica surface-treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and bisphenol F type epoxy, silica content is 25% by mass, average particle size is 10 nm, manufactured by Admatex Co., Ltd., the values ​​in Table 1 are the mass of silica, the mass of bisphenol F type epoxy resin is added to YDF-8170. Curing accelerator (D) CG1400: Product name is AMICURE CG1400, dicyandiamide, manufactured by Evonik Japan Co., Ltd. 2P4MZ (product name): 2-phenyl 4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd. Coupling agent (E) KBM-403 (product name): 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Other components (F) Black 4: Product name is "Special Black 4 "powder", carbon black, manufactured by Orion Engineered Carbon.

[0085] (Evaluation 1: Measurement of sphericity and roundness of zeolite) The sphericity of the zeolite was calculated as "minimum diameter / maximum diameter". The minimum and maximum diameters of the zeolite were determined by observation using an electrolytic emission scanning electron microscope (FE-SEM) MERLIN (manufactured by Carl Zeiss). The sphericity was calculated as the average value of 10 arbitrary particles obtained by scanning electron microscopy.

[0086] The roundness of zeolite is calculated as "4 × π × area / (circumference)". ２ The calculations were performed using the following method. The area and circumference of the zeolite were determined by observation using a scanning electron microscope (SEM). The roundness was calculated as the average value of 10 arbitrary particles obtained by the scanning electron microscope (SEM).

[0087] (Evaluation 2: Measurement of Zeolite CTE) A resin composition was prepared by removing Zeolite A from Example 1, and the coefficient of thermal expansion (CTE) of the cured product in the range of 0 to 20°C was measured. The measurement method and conditions were the same as those for Evaluation 4 described below. Subsequently, the CTE of the cured epoxy resin composition of Example 1 was also measured in the same manner. Furthermore, based on the ROM (Rule of Mixture) model of the following formula, the CTE of Zeolite A was calculated from the volume fraction of Zeolite A and the other materials. The CTEs of Zeolites B to D were also measured and calculated in the same manner. αc = αfφ + αm(1-φ) ... (Formula) αc: CTE of the resin composition αf: CTE of the zeolite αm: CTE of the resin composition φ: Volume fraction of the zeolite

[0088] (Evaluation 3: 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 spindle SC4-14) with the liquid temperature of the epoxy resin composition set to 25°C and the viscosity measured when the viscometer was rotated at 50 rpm for 1 minute. The results are shown in Table 1 under "Viscosity at 25°C (Pa·s)".

[0089] (Evaluation 4: Measurement of the coefficient of thermal expansion CTE) The epoxy resin compositions of the examples and comparative examples were measured at 7 kg / cm². ２ Under pressure, the material was cured at 165°C for 2 hours to produce a cylindrical test specimen (cured product) with a diameter of 8 mm and a height of 20 mm. The coefficient of thermal expansion (CTE) of this test specimen was measured by thermomechanical analysis (TMA) using a TMA4000SE (manufactured by NETZSCH Corporation). The measurement was performed under the following conditions: Purge gas: Air Measurement mode: Compression Load: 1 g Number of temperature scans: 2 First scan measurement temperature: Room temperature to 220°C Heating rate: 20°C / min Second scan measurement temperature: -30°C to 260°C Heating rate: 5°C / min

[0090] The first scan was performed to release the internal stress during hardening of the specimen. The data from the second scan was used to calculate the CTE. The CTE in the range of 0 to 20°C was calculated as "CTE less than Tg". The CTE in the range of 180 to 200°C was calculated as "CTE greater than or equal to Tg". The results are listed in Table 1 as "CTE less than Tg (ppm / °C)" and "CTE greater than or equal to Tg (ppm / °C)".

[0091] (Evaluation 5: Measurement of adhesive strength) The epoxy resin compositions of the examples and comparative examples were stencil-printed onto an FR4 substrate to a diameter of 2 mm. Then, a 2 mm × 2 mm × 625 μm silicon chip with SiN passivation was placed so that the passivation surface was in contact with the epoxy resin composition, and pressure was applied from above to ensure a uniform film thickness of the epoxy resin composition, followed by a bonding strength of 7 kg / cm². ２ The epoxy resin was cured at 165°C for 2 hours under pressure. The adhesive strength of the obtained test specimens and the adhesive strength after performing a PCT (Pressure Cooker Test) on the same specimens were measured. The PCT conditions were 121°C / 100% RH / 2 atm / 20 hours. A DAGE4000 bond tester manufactured by Nordoson Dage was used to measure the adhesive strength. The FR4 substrate side of the test specimen was fixed to the base of the bond tester, and stress was applied to the silicon chip in the shear direction so that the bond tester tool was parallel to one side of the silicon chip. The stress at which the chip peeled off from the FR4 was defined as the adhesive strength of the epoxy resin composition. The measurements were performed under the following conditions. The results are recorded in "Adhesive Strength (N)" in Table 1. The adhesive strength of the test specimen before PCT is recorded in the "Initial" column, and the adhesive strength of the test specimen after PCT is recorded in the "After PCT" column. [Measurement conditions] Measurement mode: shearing Tool height: 100 μm Tool speed: 200 μm / sec

[0092] (Evaluation 6: Fracture toughness (K) ＩＣ Fracture toughness (K) in the cured epoxy resin compositions of the examples and comparative examples ＩＣ The following measurements were taken in accordance with ASTM D5045-99. The epoxy resin composition was measured at 7 kg / cm³. ２Under pressure, the specimen was cured at 165°C for 2 hours to prepare a specimen measuring 14 mm wide x 75 mm long x 7 mm thick. A pre-crack with a length of 7.4 to 8.3 mm was introduced in the short axis direction using a rotary blade and a cutter blade, approximately in the center of the 75 mm long x 7 mm thick surface of the specimen. When introducing the pre-crack, the length of the pre-crack made by the rotary blade was set to 6.7 mm to 7.3 mm, and the length of the pre-crack made by the cutter blade was set to 0.5 to 1.2 mm. Subsequently, the fracture toughness value (K) of the specimen at 25°C was measured using an Autograph AGS-X (manufactured by Shimadzu Corporation). ＩＣ ) (MPa・m １／２ The following parameters were measured. The measurements were taken under the following conditions. Also, fracture toughness K ＩＣ The result was calculated using equation (1). The result is shown in Table 1 as "Fracture Toughness K". ＩＣ (MPa・m １／２ It will be recorded in )). [Measurement conditions] Distance between support points: 56 mm Head speed: 5 mm / min Fracture toughness value (K ＩＣ ) = (P / B × W ０．５ )×f(x)...(1) f(x)=6×x ０．５ ×[1.99-x(1-x)×(2.15-3.93x+2.7x ２ )] / [(1+2x)×(1-x) １．５ x = a / W P: Fracture stress (N) B: Thickness (m) W: Width (m) a: Pre-crack length

[0093]

[0094] In summary, the configuration of the present invention and its variations are described below. [1] An epoxy resin composition comprising an epoxy resin (A), an aromatic amine compound (B), and an inorganic filler (C), wherein the inorganic filler (C) comprises a zeolite (C1) having a thermal expansion coefficient of -20 to -3 ppm / °C. [2] The epoxy resin composition according to [1], wherein the epoxy resin (A) comprises at least one selected from bisphenol-type epoxy resin, aminophenol-type epoxy resin, naphthalene-type epoxy resin, and cyclohexane-type epoxy resin. [3] The epoxy resin composition according to [1] or [2], wherein the content of epoxy resin (A) is 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and / or 50% by mass or less, 45% by mass or less, 40% by mass or less, 37% by mass or less, or 35% by mass or less, or 5 to 50% by mass, 10 to 45% by mass, 15 to 40% by mass, 20 to 37% by mass, or 20 to 35% by mass. [4] The epoxy resin composition according to any one of [1] to [3], wherein the content of bisphenol-type epoxy resin relative to epoxy resin (A) (100% by mass) is 30% by mass or more, 50% by mass or more, 65% by mass or more, 75% by mass or more, or 85% by mass or more. [5] The epoxy resin composition according to any one of [1] to [4], wherein the content of aminophenol-type epoxy resin relative to epoxy resin (A) (100% by mass) is 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less. [6] The epoxy resin composition according to any one of [1] to [5], wherein the content of aliphatic epoxy resin relative to epoxy resin (A) (100% by mass) is 50% by mass or less, 30% by mass or less, 10% by mass or less, 3% by mass or less, or 1% by mass or less.[7] The epoxy resin composition according to any one of [1] to [6], wherein the aromatic amine compound (B) comprises at least one selected from the group consisting of 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-methylenebis(2-ethylaniline), diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. [8] The epoxy resin composition according to any one of [1] to [7], wherein the content of the aromatic amine compound (B) is 4% by mass or more, 6% by mass or more, 8% by mass or more, or 9% by mass or more, and / or 30% by mass or less, 25% by mass or less, 20% by mass or less, 16% by mass or less, or 14% by mass or less, or 4 to 30% by mass, 6 to 25% by mass, 8 to 20% by mass, 9 to 16% by mass, or 9 to 14% by mass. [9] The epoxy resin composition according to any one of [1] to [8], wherein the content of aromatic amine compound (B) relative to epoxy resin (A) (100% by mass) is 16% by mass or more, 20% by mass or more, 24% by mass or more, 28% by mass or more, 32% by mass or more, or 34% by mass or more, and / or 100% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less, or 16 to 100% by mass, 20 to 80% by mass, 24 to 70% by mass, 28 to 60% by mass, 32 to 50% by mass, or 34 to 50% by mass.

[10] The specific gravity of zeolite (C1) is 1.0 g / cm³. ３ Above, 1.3g / cm ３ The above, or 1.5 g / cm³ ３ The above, and / or 2.2 g / cm³ ３ Less than 2.15 g / cm³ ３ Less than 2.1 g / cm³ ３ Less than 2.0 g / cm³ ３ Less than 1.0 g / cm³ ３ 2.2g / cm or more ３ Less than 1.3 g / cm³ ３ 2.15g / cm or more ３ Less than 1.5 g / cm³ ３ 2.1g / cm or more ３ Less than 1.5 g / cm³ ３Above 2.0 g / cm ３An epoxy resin composition according to any one of [1] to [9], wherein the coefficient of thermal expansion of the zeolite (C1) is -20 ppm / °C or more, -18 ppm / °C or more, -16 ppm / °C or more, -14 ppm / °C or more, or -12 ppm / °C or more, and / or -3 ppm / °C or less, -4 ppm / °C or less, -5 ppm / °C or less, -6 ppm / °C or less, or -7 ppm / °C or less, or -20 to -3 ppm / °C, -18 to -4 ppm / °C, -16 to -5 ppm / °C, -14 to -6 ppm / °C, or -12 to -7 ppm / °C, according to any one of [1] to

[10] .

[12] The epoxy resin composition according to any one of [1] to

[11] , wherein the sphericity of the zeolite (C1) is 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, or 0.78 or more and / or 1 or less, or 0.6 to 1, 0.65 to 1, 0.7 to 1, 0.75 to 1, or 0.78 to 1.

[13] The epoxy resin composition according to any one of [1] to

[12] , wherein the roundness of the zeolite (C1) is 0.6 or more, 0.7 or more, 0.8 or more, 0.85 or more, or 0.9 or more and / or 1 or less, or 0.6 to 1, 0.7 to 1, 0.8 to 1, 0.85 to 1, or 0.9 to 1.

[14] The epoxy resin composition according to any one of [1] to

[13] , further comprising silica (C2) as an inorganic filler (C).

[15] The epoxy resin composition according to any one of [1] to

[14] , wherein the content of inorganic filler (C) is 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, and / or 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less, or 30 to 80% by mass, 35 to 75% by mass, 40 to 70% by mass, 45 to 65% by mass, or 50 to 65% by mass.

[16] The epoxy resin composition according to any one of [1] to

[15] , wherein the zeolite (C1) content is 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, and / or 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, or 55% by mass or less, or 1 to 75% by mass, 2 to 70% by mass, 3 to 65% by mass, 5 to 60% by mass, 10 to 55% by mass, or 15 to 55% by mass.

[17] The epoxy resin composition according to any one of

[14] to

[16] , wherein the silica (C2) content is 1% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more, and / or 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less, or 1 to 80% by mass, 3 to 70% by mass, 5 to 60% by mass, 10 to 50% by mass, or 10 to 40% by mass.

[18] The epoxy resin composition according to any one of [1] to

[17] , wherein the content of inorganic filler (C) relative to epoxy resin (A) (100% by mass) is 60% by mass or more, 80% by mass or more, 100% by mass or more, 120% by mass or more, or 140% by mass or more, and / or 400% by mass or less, 360% by mass or less, 320% by mass or less, 280% by mass or less, or 240% by mass or less, or 60 to 400% by mass, 80 to 360% by mass, 100 to 320% by mass, 120 to 280% by mass, or 140 to 240% by mass.

[19] The epoxy resin composition according to any one of [1] to

[18] , wherein the content of zeolite (C1) relative to epoxy resin (A) (100% by mass) is 5% by mass or more, 10% by mass or more, 15% by mass or more, 25% by mass or more, or 40% by mass or more, and / or 320% by mass or less, 280% by mass or less, 240% by mass or less, 200% by mass or less, or 160% by mass or less, or 5 to 320% by mass, 10 to 280% by mass, 15 to 240% by mass, 25 to 200% by mass, or 40 to 160% by mass.

[20] The epoxy resin composition according to any one of

[14] to

[19] , wherein the silica (C2) content relative to epoxy resin (A) (100% by mass) is 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 25% by mass or more, 35% by mass or more, or 45% by mass or more, and / or 320% by mass or less, 240% by mass or less, 200% by mass or less, 160% by mass or less, or 120% by mass or less, or 4 to 320% by mass, 8 to 240% by mass, 12 to 200% by mass, 16 to 160% by mass, 25 to 120% by mass, 35 to 120% by mass, or 45 to 120% by mass.

[21] The epoxy resin composition according to any one of [1] to

[20] , wherein the content of zeolite (C1) relative to inorganic filler (C) (100% by mass) is 4% by mass or more, 8% by mass or more, 16% by mass or more, 24% by mass or more, or 30% by mass or more, and / or 100% by mass or less, 90% by mass or less, 80% by mass or less, or 70% by mass or less, or 4 to 100% by mass, 8 to 90% by mass, 16 to 80% by mass, 24 to 70% by mass, or 30 to 70% by mass.

[22] The epoxy resin composition according to any one of [1] to

[21] , further comprising a curing accelerator (D), wherein the curing accelerator (D) comprises at least one imidazole-based curing accelerator selected from the group consisting of 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

[23] The epoxy resin composition according to

[22] , wherein the content of the curing accelerator (D) is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and / or 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less, or 0.001 to 3% by mass, 0.01 to 2% by mass, 0.05 to 1% by mass, or 0.1 to 0.5% by mass.

[24] The epoxy resin composition according to any one of [1] to

[23] , further comprising a coupling agent (E), wherein the content of the coupling agent (E) is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.15% by mass or more, or 0.2% by mass or more, and / or 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less, or 0.01 to 3% by mass, 0.05 to 2% by mass, 0.1 to 1% by mass, 0.15 to 0.5% by mass, or 0.2 to 0.5% by mass.

[25] The epoxy resin composition according to any one of [1] to

[24] , wherein the content of the solvent is 5% by mass or less, 1% by mass or less, 0.1% by mass or less, or 0.01% by mass or less, and / or 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more.

[26] The epoxy resin composition according to any one of [1] to

[25] , wherein the viscosity at 25°C is 2.5 Pa·s or more, 3.0 Pa·s or more, 6.0 Pa·s or more, or 9.0 Pa·s or more, and / or 500 Pa·s or less, 400 Pa·s or less, 300 Pa·s or less, 200 Pa·s or less, or 100 Pa·s or less, or 2.5 to 500 Pa·s, 3.0 to 400 Pa·s, 6.0 to 300 Pa·s, 9.0 to 200 Pa·s, or 9.0 to 100 Pa·s.

[27] The epoxy resin composition according to any one of [1] to

[26] , wherein the CTE (ppm / °C) below Tg in the cured product is 15 to 31 ppm / °C, or 20 to 30 ppm / °C.

[28] The epoxy resin composition according to any one of [1] to

[27] , wherein the cured product has a CTE (ppm / °C) of Tg or higher that is 40 to 120 ppm / °C or 60 to 111 ppm / °C.

[29] The epoxy resin composition according to any one of [1] to

[28] , wherein the cured product has an adhesive strength (initial adhesive strength) of 280 N or more, 290 to 600 N, 300 to 500 N, or 310 to 400 N.

[30] The epoxy resin composition according to any one of [1] to

[29] , wherein the cured product has an adhesive strength after PCT of 180 N or more, 200 to 500 N, 220 to 400 N, or 230 to 320 N.

[31] The cured product has a fracture toughness KIC (MPa·m). １／２ ) is 2.1 MPa·m１／２ Above, 2.1~5MPa・m １／２ , or 2.2 to 4 MPa·m １／２ [1] to

[30] is an epoxy resin composition according to any one of the following:

[32] An epoxy resin composition according to any one of the following: [1] to

[31] for semiconductor encapsulation.

[33] An epoxy resin composition according to any one of the following: [1] to

[31] for underfill material.

[34] A cured product of the epoxy resin composition according to any one of the following: [1] to

[33] .

[35] A semiconductor device comprising: a substrate; a semiconductor element disposed on the substrate; and a cured product according to

[34] for encapsulating the semiconductor element.

[36] A method for manufacturing a semiconductor device comprising: filling the gap between the substrate and the semiconductor element disposed on the substrate with an epoxy resin composition according to any one of the following: [1] to

[31] ; and heating the epoxy resin composition to cure it.

Claims

1. An epoxy resin composition comprising an epoxy resin (A), an aromatic amine compound (B), and an inorganic filler (C), wherein the inorganic filler (C) comprises a zeolite (C1) having a thermal expansion coefficient of -20 to -3 ppm / °C.

2. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) comprises at least one selected from bisphenol-type epoxy resin, aminophenol-type epoxy resin, naphthalene-type epoxy resin, and cyclohexane-type epoxy resin.

3. The epoxy resin composition according to claim 1 or 2, further comprising silica (C2) as an inorganic filler (C).

4. The epoxy resin composition according to claim 1 or 2, wherein the content of zeolite (C1) relative to inorganic filler (C) (100% by mass) is 30% by mass or more.

5. The epoxy resin composition according to claim 1 or 2, wherein the sphericity of the zeolite (C1) is 0.6 or higher.

6. The epoxy resin composition according to claim 1 or 2, for use in semiconductor encapsulation.

7. The epoxy resin composition according to claim 1 or 2, which is an underfill material.

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

9. A semiconductor device comprising: a substrate; a semiconductor element disposed on the substrate; and a cured product according to claim 8 for sealing the semiconductor element.

10. A method for manufacturing a semiconductor device, comprising the steps of: filling the gap between a substrate and a semiconductor element disposed on the substrate with the epoxy resin composition described in claim 1 or 2; and heating and curing the epoxy resin composition.

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