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

Abstract

The present invention provides an epoxy resin composition that is less prone to wafer warping after molding. [Solution] An epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), An epoxy resin composition comprising epoxy resin (A1), which has a glycidyl ether group and polyethylene glycol groups and / or polypropylene glycol groups, as epoxy resin (A).

Description

[Technical Field]

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

[0002] Generally, semiconductor elements such as integrated circuits that make up semiconductor devices are used in a form sealed with an encapsulating material. There are several methods for encapsulating semiconductor elements, and one of them is compression molding. Compression molding is a method in which an encapsulating material consisting of a liquid or granular resin composition is placed in a mold, heated and melted as needed, and compressed to form the object. In recent years, the opportunities to use compression molding for encapsulating semiconductor elements have been increasing. This is due to the spread of wafer-level chip-size packaging technology. This technology involves performing compression molding using an encapsulating material (compression molding material) at the wafer stage, curing it to encapsulate a large number of semiconductor elements at once, and then separating them into individual pieces.

[0003] Conventional compression molding methods primarily use solid (granular) curable resin compositions. However, with the recent development of new compression molding technologies, liquid curable resin compositions are increasingly being used. These liquid curable resin compositions are called liquid compression molding (LCM) materials and are useful from the standpoint of balancing various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness.

[0004] Compared to methods that encapsulate semiconductor elements after individual component separation, wafer-level chip-size packaging offers higher productivity, but it has the problem of wafers being prone to warping after molding (after encapsulation). When wafer warping occurs, it can have adverse effects in subsequent processes such as transport, grinding, and individual component separation, such as insufficient wafer fixation, which can lead to a decrease in the reliability of semiconductor devices.

[0005] To solve these problems, various sealing materials have been investigated. For example, Patent Document 1 discloses a liquid compression molding material for sealing, which is a liquid epoxy resin composition at room temperature that is used as a sealing material by applying it to the surface of components constituting electronic components or semiconductor devices and then heating and curing it, characterized in that the glass transition temperature of the cured product is less than 40°C, and the coefficient of linear expansion of the cured product at temperatures lower than the glass transition temperature is 5 ppm / °C or more and less than 15 ppm / °C. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2006-232950 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, even when these epoxy resin compositions were used as LCM materials, warping sometimes occurred in the wafers after molding (after sealing).

[0008] Therefore, an object of the present invention is to provide an epoxy resin composition that is less prone to wafer warping after molding (after sealing). Another object is to provide a cured product of the epoxy resin composition, a semiconductor device comprising the cured product, and a method for manufacturing the same. [Means for solving the problem]

[0009] The inventors, through diligent research to achieve the above objectives, discovered that the above problems can be solved by incorporating specific components into an epoxy resin composition. This invention was completed based on these findings.

[0010] In other words, the present invention provides an epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), Provided is an epoxy resin composition containing an epoxy resin (A1) having a glycidyl ether group and a polyethylene glycol group and / or a polypropylene glycol group.

[0011] The epoxy resin (A1) is represented by the formula (1)

Chemical formula

Chemical formula

[0012] The epoxy resin (A1) is represented by the formula (3)

Chemical formula

Chemical formula

[0013] The above epoxy resin composition preferably contains an imidazole-based curing accelerator as the curing accelerator (B).

[0014] The epoxy equivalent of the epoxy resin (A1) is preferably 300 to 1100 g / eq.

[0015] The content of epoxy resin (A1) relative to epoxy resin (A) (100% by mass) is preferably 1 to 50% by mass.

[0016] The above epoxy resin composition preferably further contains an epoxy resin (A2) other than epoxy resin (A1) as epoxy resin (A).

[0017] The content of epoxy resin (A1) relative to epoxy resin (A2) (100% by mass) is preferably 1 to 65% by mass.

[0018] It is preferable that the epoxy resin (A2) includes a bisphenol F type epoxy resin.

[0019] It is preferable that the epoxy resin (A2) includes an aminophenol-type epoxy resin.

[0020] The epoxy resin composition described above is preferably a liquid compression molding material.

[0021] The present invention also provides a cured product of the above epoxy resin composition.

[0022] The present invention also provides a semiconductor device comprising the above-mentioned cured material.

[0023] In this invention, a support and A semiconductor element mounted on the above support, The cured material used to enclose the semiconductor element, We also provide semiconductor devices equipped with these features.

[0024] In this invention, a support and A step of supplying the epoxy resin composition to a laminate comprising a semiconductor element mounted on the support mentioned above, The process involves filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a sealed body. We also provide a method for manufacturing a semiconductor device that includes this device. [Effects of the Invention]

[0025] The epoxy resin composition of the present invention is less prone to wafer warping after molding. Therefore, semiconductor devices equipped with cured products of the above epoxy resin composition exhibit high reliability. [Brief explanation of the drawing]

[0026] [Figure 1] This figure illustrates one embodiment of the method for manufacturing a semiconductor device according to the present invention. [Figure 2] This figure illustrates another embodiment of the method for manufacturing a semiconductor device according to the present invention. [Figure 3] This is a cross-sectional SEM image of the side surface of the chip of Comparative Example 1. [Figure 4] This figure shows an embodiment of a semiconductor device that applies 2.5-dimensional stacking technology. [Figure 5] This figure shows an embodiment of a semiconductor device that utilizes 3D stacking technology. [Modes for carrying out the invention]

[0027] <Epoxy resin composition> The epoxy resin composition of the present invention comprises an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), wherein the epoxy resin (A) includes an epoxy resin (A1) having a glycidyl ether group and a polyethylene glycol group and / or a polypropylene glycol group. The epoxy resin composition may further contain a curing agent (D).

[0028] • Epoxy resin (A) The above epoxy resin composition, by containing epoxy resin (A), can impart high electrical insulation properties to its cured product. 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.

[0029] In the epoxy resin composition described above, the content of epoxy resin having three or more epoxy groups is preferably 60% by mass or less relative to epoxy resin (A) (100% by mass). When the content of epoxy resin having three or more epoxy groups is within the above range, the curability is improved and the crack resistance of the cured product tends to improve.

[0030] 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.

[0031] In the epoxy resin composition described above, the liquid epoxy resin content is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, relative to epoxy resin (A) (100% by mass).

[0032] 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, and oxazolides. Examples include ecliptic resins containing ecliptic rings, glycidylamine-type ecliptic resins, glycidyl ester-type ecliptic resins, cresol novolac-type ecliptic resins, biphenyl-type ecliptic resins, fluorene-type ecliptic resins, biphenyl aralkyl ecliptic resins, aliphatic ecliptic resins (e.g., epoxidized polybutadiene), ecliptic resins having a butadiene structure, alicyclic ecliptic resins, heterocyclic ecliptic resins, spiro-ring-containing ecliptic resins, cyclohexanedimethanol-type ecliptic resins, naphthylene ether-type ecliptic resins, trimethylol-type ecliptic resins, tetraphenylmethane-type ecliptic resins, aminophenol-type ecliptic resins, and silicone-modified ecliptic resins.

[0033] The above epoxy resin composition includes epoxy resin (A1) as epoxy resin (A), which has a glycidyl ether group and polyethylene glycol groups and / or polypropylene glycol groups. Epoxy resin (A1) may be used alone or in combination of two or more types.

[0034] The number of glycidyl ether groups in epoxy resin (A1) is not particularly limited; for example, it may be 1 or 2 or more. However, from the viewpoint of the epoxy resin composition exhibiting excellent curability and increasing the glass transition temperature of the cured product, it is preferable to have 2 or 3 glycidyl ether groups. In other words, epoxy resin (A1) is preferably an epoxy resin having 2 or 3 glycidyl ether groups.

[0035] The addition of epoxy resin (A1) to the epoxy resin composition suppresses wafer warping after molding. Although the reason is not entirely clear, it is thought that the addition of epoxy resin (A1) improves the flexibility of the cured product of the epoxy resin composition, thereby reducing the force exerted on the wafer due to curing shrinkage (the force that tends to cause the wafer to warp). The reason why the cured product exhibits flexibility is thought to be due to the polyethylene glycol groups and polypropylene glycol groups present in epoxy resin (A1). In other words, because epoxy resin (A1) has a long-chain backbone such as polyethylene glycol groups and polypropylene glycol groups in its molecule, its cured product can be said to have appropriate flexibility.

[0036] From the viewpoint of suppressing wafer warping, the epoxy resin (A1) is preferably an epoxy resin having an alkyl group with 5 to 30 carbon atoms (preferably 10 to 15 carbon atoms) or a bisphenol-type epoxy resin. Furthermore, the epoxy resin (A1) is more preferably an epoxy resin (A1-1) represented by the following formula (1) or an epoxy resin (A1-2) represented by the following formula (2).

[0037] [ka] [ka]

[0038] In formula (1), R represents an alkyl group having 10 to 15 carbon atoms. X represents a polyethylene glycol group or a polypropylene glycol group. The average degree of polymerization of the polyethylene glycol group or polypropylene glycol group of X is not particularly limited, but is preferably 2 to 20, more preferably 5 to 18, even more preferably 8 to 16, and particularly preferably 10 to 15. The above-mentioned "average degree of polymerization" refers to the average degree of polymerization when viewed from alkylene glycol. For example, the average degree of polymerization of diethylene glycol is 2, and the average degree of polymerization of triethylene glycol is 3. By including epoxy resin (A1-1) as epoxy resin (A), the warping of the wafer after molding is suppressed, and the gap-filling ability of the epoxy resin composition can be improved. The reason for this is not clear, but it is thought to be a characteristic resulting from the viscosity of the epoxy resin composition decreasing due to having a long-chain skeleton. In particular, the epoxy resin composition of the present invention exhibits excellent filling properties for narrow gaps (for example, gaps of 1 to 100 μm are preferred, more preferably 3 to 60 μm, even more preferably 5 to 50 μm, and particularly preferably 10 to 40 μm). "Gap filling properties" refer to the filling properties of the epoxy resin composition for the gap between a support (e.g., a substrate) and a semiconductor element mounted on the support. The same applies throughout this specification.

[0039] In formula (2), Y and Z are the same or different and represent a polyethylene glycol group or a polypropylene glycol group. The average degree of polymerization of the polyethylene glycol groups or polypropylene glycol groups of Y and Z is not particularly limited, but is preferably 2 to 20, more preferably 3 to 16, and even more preferably 4 to 12. By including epoxy resin (A1-2) as epoxy resin (A), warping of the wafer after molding is suppressed, delamination of the cured product (sealant) from the object to be sealed, such as a chip, during molding (hereinafter referred to as "delamination") is suppressed, and the durability of the cured product is improved. The reason why delamination is suppressed is not clear, but it is thought to be a characteristic caused by the small curing shrinkage of epoxy resin (A1-2) compared to other epoxy resins. The reason why epoxy resin (A1-2) has small curing shrinkage is thought to be due to the inclusion of flexible structures such as polyethylene glycol groups or polypropylene glycol groups in its molecule. The reason why the durability of the cured product is improved is also not clear, but it is thought to be due to the presence of a rigid structure called a bisphenol skeleton in its molecule.

[0040] The epoxy resin (A1) is more preferably the epoxy resin (A1-3) represented by the following formula (3), or the epoxy resin (A1-4) represented by the following formula (4). Note that the epoxy resin (A1-3) is a specific specification of X in the epoxy resin (A1-1). The epoxy resin (A1-4) is a specific specification of Y and Z in the epoxy resin (A1-2).

[0041] [ka] [ka]

[0042] In formula (3), R represents an alkyl group having 10 to 15 carbon atoms, and l is 10 to 20. Including epoxy resin (A1-3) as epoxy resin (A) tends to further suppress wafer warping after molding and further improve the gap-filling ability of the epoxy resin composition. The reason for this is not clear, but it is thought to be due to the fact that epoxy resin (A1-3) has a long-chain skeleton, which reduces the viscosity of the epoxy resin composition, and that it has polyethylene glycol groups of appropriate length, which further improves the flexibility of the cured product.

[0043] In equation (4), m represents an integer greater than or equal to 2. n represents an integer greater than or equal to 2. m+n represents a value between 4 and 12. By including epoxy resin (A1-4) as epoxy resin (A), the warping of the wafer after molding is further suppressed, delamination can be suppressed, and the durability of the cured product can be further improved. The reason why delamination is suppressed is not clear, but it is thought to be due to the fact that epoxy resin (A1-4) has a small curing shrinkage compared to other epoxy resins. The reason why epoxy resin (A1-4) has a small curing shrinkage is thought to be due to the presence of polypropylene glycol groups in the molecule, which are a structure that exhibits flexibility. The reason why the durability of the cured product is improved is not clear, but it is thought to be due to the fact that, in addition to having a rigid structure called a bisphenol skeleton in the molecule, it also has a flexible structure called a polypropylene glycol group, resulting in a good balance between appropriate rigidity and flexibility. Among these characteristics, when m+n is between 8 and 12, a strong delamination suppression effect tends to be exhibited. Furthermore, when m+n is between 4 and 7, warping of the cured product is suppressed, and the durability of the cured product tends to improve.

[0044] The epoxy equivalent of the epoxy resin (A1) is not particularly limited, but is preferably 300 to 1100 g / eq, more preferably 300 to 600 g / eq, and even more preferably 300 to 550 g / eq.

[0045] The epoxy resin composition described above may further contain an epoxy resin (A2) other than epoxy resin (A1) as epoxy resin (A). Epoxy resin (A2) is an epoxy resin other than epoxy resin (A1) having a glycidyl ether group and a polyethylene glycol group and / or a polypropylene glycol group. Examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin (excluding those containing polyethylene glycol groups and polypropylene glycol groups in the molecule), aminophenol type epoxy resin, glycidylamine type epoxy resin, and aliphatic epoxy resin. From the viewpoint of suppressing wafer warping after molding, it is preferable that the epoxy resin composition contains a bisphenol type epoxy resin (particularly bisphenol F type epoxy resin) as epoxy resin (A2). Furthermore, from the viewpoint of increasing the glass transition temperature and handling, it is preferable that the epoxy resin composition contains at least one selected from the group consisting of aminophenol type epoxy resin and glycidylamine type epoxy resin as epoxy resin (A2). Epoxy resin (A2) may be used alone or in combination of two or more types.

[0046] Specific examples of liquid epoxy resins include "YDF-8170" and "YDF-870GS" (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" (both naphthalene type epoxy resins) from DIC Corporation; and "jER828US" and "jER828EL" (both bisphenol A type epoxy resins), "jER806," and "jER80" from Mitsubishi Chemical Corporation. 7 (all are bisphenol F type epoxy resins), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD" (all are aminophenol type epoxy resins, also glycidylamine type epoxy resins), "YX7400N" (aliphatic epoxy resin / diglycidyl ether of polytetramethylene glycol); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin), "EX-171" (lauryl alcohol (EO) 15 Examples include glycidyl ethers, "ADEKA Resin EP-4005" and "ADEKA Resin EP-4003S" (both bisphenol A type epoxy resins containing polypropylene glycol structure) from ADEKA Corporation, "EP-3950L" (aminophenol type epoxy resin), and "EP3980S" (glycidylamine type epoxy resin); "AER9000" (PO-modified bisphenol type epoxy resin), "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins) from Asahi Kasei Corporation; "DER852" and "DER858" (both oxazolidone ring-containing epoxy resins) from Dow Chemical Ltd., "FAE-2500" and "EPPN-501HY" (both trisphenolmethane type epoxy resins) from Nippon Kayaku Co., Ltd., and "Celoxide 2021P" (alicyclic epoxy resin) from Daicel Corporation.

[0047] 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.

[0048] The epoxy resin composition described above may contain an alicyclic epoxy resin as epoxy resin (A), but it is preferable to omit it because it tends to reduce the curability.

[0049] The content of epoxy resin (A) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 9% by mass or more, and particularly preferably 12% by mass or more. Also, for example, it is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. When the content of epoxy resin (A) is within the above range, a cured product with high electrical insulation properties tends to be obtained. From a similar viewpoint, the content of epoxy resin (A) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 3 to 60% by mass, more preferably 6 to 40% by mass, even more preferably 9 to 30% by mass, even more preferably 9 to 25% by mass, and particularly preferably 12 to 20% by mass.

[0050] The content of epoxy resin (A1) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.6% by mass or more, even more preferably 0.8% by mass or more, and particularly preferably 1% by mass or more. Also, for example, it is preferably 30% by mass or less, 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. When the content of epoxy resin (A1) is within the above range, the warping of the wafer after molding tends to be further suppressed. From a similar viewpoint, the content of epoxy resin (A1) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 0.1 to 30% by mass, more preferably 0.3 to 15% by mass, even more preferably 0.6 to 10% by mass, even more preferably 0.8 to 8% by mass, and particularly preferably 1 to 6% by mass.

[0051] The content of epoxy resin (A2) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 6% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more. Also, for example, 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 16% by mass or less. When the content of epoxy resin (A2) is within the above range, the warping of the wafer after molding tends to be further suppressed. From a similar viewpoint, the content of epoxy resin (A2) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, even more preferably 6 to 25% by mass, even more preferably 8 to 20% by mass, and particularly preferably 10 to 16% by mass.

[0052] The content of epoxy resin (A1) relative to epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 6% by mass or more. Also, is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the content of epoxy resin (A1) is within the above range, the warping of the wafer after molding tends to be further suppressed. From a similar viewpoint, the content of epoxy resin (A1) relative to epoxy resin (A) (100% by mass) is not particularly limited, but is preferably 1 to 80% by mass, more preferably 3 to 60% by mass, even more preferably 5 to 50% by mass, even more preferably 6 to 40% by mass, and particularly preferably 6 to 30% by mass.

[0053] The content of epoxy resin (A1) relative to epoxy resin (A2) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 6% by mass or more. Also, is preferably 80% by mass or less, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less. When the content of epoxy resin (A1) is within the above range, the warping of the wafer after molding tends to be further suppressed. From a similar viewpoint, the content of epoxy resin (A1) relative to epoxy resin (A2) (100% by mass) is not particularly limited, but is preferably 1 to 80% by mass, more preferably 3 to 65% by mass, even more preferably 5 to 60% by mass, even more preferably 6 to 50% by mass, even more preferably 6 to 45% by mass, and particularly preferably 6 to 40% by mass.

[0054] The content of epoxy resin (A1) in the above epoxy resin composition, i.e., the total amount (100% by mass) of the resin components, namely epoxy resin (A), curing accelerator (B), and curing agent (D), 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 4% by mass or more, and particularly preferably 5% by mass or more. Also, for example, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. When the content of epoxy resin (A1) is within the above range, the warping of the wafer after molding tends to be further suppressed. From a similar viewpoint, the content of epoxy resin (A1) in relation to the total amount (100% by mass) of the resin components is not particularly limited, but is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, even more preferably 3 to 35% by mass, even more preferably 4 to 30% by mass, and particularly preferably 5 to 25% by mass.

[0055] • Curing accelerator (B) The curing accelerator (B) has the property of accelerating the curing of the epoxy resin. The curing accelerator (B) is not particularly limited, but examples include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphorus-based curing accelerators, and dicyandiamide. Among these, imidazole-based curing accelerators are preferred from the viewpoint of suppressing wafer warping after molding and from the viewpoint of reliability. The curing accelerator (B) can be used alone or in combination of two or more types.

[0056] Examples of imidazole-based curing accelerators include imidazole compounds 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, 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)benzimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. Commercially available products include 2-ethyl-4-methylimidazole (product name "2E4MZ"), 2-phenyl-4-methylimidazole (product name "2P4MZ"), 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name "2P4MHZ-PW"), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product name "2MZA-PW"), "2MZ-OK", "2MA-OK", and "2PHZ", all manufactured by Shikoku 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.).

[0057] Examples of tertiary amine-based curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N'-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene, 1,5-diazabicyclo[4.3.0]nonene, and salts thereof. Examples of the salts include 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.

[0058] Examples of phosphorus-based curing accelerators include phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium-tetraphenylborate, triphenylphosphine-triphenylborane, and 1,2-bis-(diphenylphosphine)ethane.

[0059] The content of the curing accelerator (B) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.4% 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 8% by mass or less, even more preferably 6% by mass or less, even more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the content of the curing accelerator (B) is within the above range, the warping of the wafer after molding is further suppressed, and the curability is improved, resulting in better mold forming. From a similar viewpoint, the content of the curing accelerator (B) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, even more preferably 0.1 to 10% by mass, even more preferably 0.2 to 8% by mass, even more preferably 0.4 to 6% by mass, even more preferably 0.4 to 4% by mass, even more preferably 0.4 to 3% by mass, even more preferably 0.4 to 2% by mass, and particularly preferably 0.4 to 1% by mass.

[0060] The content of the curing accelerator (B) relative to the epoxy resin (A) (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, even more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 2.5% by mass or more. Also, is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% 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. When the content of the curing accelerator (B) is within the above range, the warping of the wafer after molding is further suppressed, and the curability is improved, resulting in better mold forming. From a similar viewpoint, the content of the curing accelerator (B) relative to the epoxy resin (A) (100% by mass) is not particularly limited, but is preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass, even more preferably 1 to 40% by mass, even more preferably 2 to 30% by mass, even more preferably 2.5 to 20% by mass, even more preferably 2.5 to 10% by mass, even more preferably 2.5 to 8% by mass, and particularly preferably 2.5 to 6% by mass.

[0061] ·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 these properties.

[0062] 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 or alumina is preferred from the viewpoint of achieving a high filler content. One type of inorganic filler (C) can be used alone, or two or more types can be used in combination.

[0063] 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 (especially a phenylamino group) to improve its dispersibility and compatibility with the epoxy resin, thereby bringing the viscosity of the epoxy resin composition within an appropriate range. Examples of the coupling agent include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. One of the above coupling agents can be used alone for surface treatment of the inorganic filler (C), or two or more can be used in combination.

[0064] Commercially available inorganic fillers (C) include "YA050C-SM1" (silicon dioxide surface treated with 3-methacryloxypropyltrimethoxysilane, average particle size 0.05 μm), "SE1050-SMO" (silicon dioxide surface treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.3 μm), "SE101G-SMO" (methacrylic surface-treated silica filler, average particle size 0.2 μm, manufactured by Admatex), and "SE605H-SMG" (methacrylic surface-treated silica filler, average particle size 1.8 μm, manufactured by Admatex), all manufactured by Admatex.

[0065] 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.

[0066] 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 7 μm, even more preferably 10 nm to 5 μm, and particularly preferably 30 nm to 3 μm. Because the average particle size of the inorganic filler (C) is within the above range, the particle size is not too large, and the epoxy resin composition tends to have high filling properties even in narrow gaps. In addition, two or more fillers with different average particle sizes may be used in combination to adjust the viscosity of the epoxy resin composition. In this specification, the method for measuring the average particle size of the inorganic filler (C) is not particularly limited, but can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0067] When the epoxy resin composition contains silica as an inorganic filler (C), it is preferable to use a first silica with an average particle size of 10 nm or more and less than 100 nm, and a second silica with an average particle size of 0.1 to 5.0 μm. When the epoxy resin composition contains alumina as an inorganic filler (C), it is preferable that its average particle size is 0.1 to 5.0 μm.

[0068] The content of inorganic filler (C) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it 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, and particularly preferably 74% by mass or more. Alternatively, for example, it is preferably 90% by mass or less, more preferably 88% by mass or less, even more preferably 86% by mass or less, and particularly preferably 85% by mass or less. When the content of inorganic filler (C) is within the above range, the viscosity of the epoxy resin composition becomes within an appropriate range, improving gap filling and workability, and tending to further suppress wafer warping after molding. From a similar viewpoint, the content of inorganic filler (C) in the epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 30 to 90% by mass, more preferably 50 to 88% by mass, even more preferably 60 to 88% by mass, even more preferably 70 to 86% by mass, and particularly preferably 74 to 85% by mass.

[0069] 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 100% by mass or more, more preferably 200% by mass or more, even more preferably 300% by mass or more, even more preferably 350% by mass or more, and particularly preferably 400% by mass or more. Alternatively, it is preferably 800% by mass or less, more preferably 700% by mass or less, even more preferably 650% by mass or less, even more preferably 600% by mass or less, and particularly preferably 550% by mass or less. When the content of inorganic filler (C) is within the above range, the viscosity of the epoxy resin composition becomes appropriate, improving gap filling and workability, and tends to further suppress wafer warping after molding. From a similar viewpoint, the content of inorganic filler (C) relative to epoxy resin (A) (100% by mass) is not particularly limited, but is preferably 100 to 800% by mass, more preferably 200 to 700% by mass, even more preferably 300 to 650% by mass, even more preferably 350 to 600% by mass, and particularly preferably 400 to 550% by mass.

[0070] • Hardener (D) The epoxy resin composition described above may contain a curing agent (D). The curing agent (D) is not particularly limited as long as it initiates, promotes, or accelerates the polymerization of the epoxy resin, but examples include acid anhydride-based curing agents, phenol-based curing agents, and amine-based curing agents. One type of curing agent (D) may be used alone, or two or more types may be used in combination.

[0071] Examples of the above acid anhydride-based curing agents include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadoic anhydride. Examples of the above phenol-based curing agents include phenol novolac resin, cresol novolac resin, naphthol-modified phenol resin, dicyclopentadiene-modified phenol resin, and p-xylene-modified phenol resin. Examples of the above amine-based curing agents include aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone.

[0072] The epoxy resin composition described above may contain a curing agent (D) that includes a urethane bond, but it is preferable that it does not contain a urethane bond from the viewpoint of curability and filling properties. Examples of curing agents that include a urethane bond include blocked polyurethane and microencapsulated isocyanate-based latent curing agents. Blocked polyurethane refers to a compound obtained by blocking the active isocyanate groups at the ends of a urethane prepolymer obtained by reacting a polyhydroxy compound such as a polyether polyol or polyester polyol with a polyisocyanate using an active hydrogen compound (blocking agent). Microencapsulated isocyanate-based latent curing agents refer to microencapsulated epoxy resin curing agents that have a structure derived from an isocyanate compound.

[0073] The content of the curing agent (D) 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 0.2% by mass or more, and particularly preferably 0.5% by mass or more. Alternatively, it is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. When the content of the curing agent (D) is within the above range, the curability tends to improve and mold molding tends to be good. From a similar viewpoint, the content of the curing agent (D) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, even more preferably 0.1 to 3% by mass, even more preferably 0.2 to 3% by mass, and particularly preferably 0.5 to 2% by mass.

[0074] • Alcohol compounds (E) having a polytetramethylene ether structure within the molecule The epoxy resin composition described above may contain an alcohol compound (E) having a polytetramethylene ether structure within its molecule. The epoxy resin composition described above tends to be less prone to warping of the wafer after molding (after sealing) due to the inclusion of the alcohol compound (E).

[0075] Examples of alcohol compounds having a polytetramethylene ether structure within the above molecule include polycarbonate diol compounds having a tetramethylene glycol structure as an alkylene glycol structure, and polytetramethylene ether glycols. Examples of commercially available alcohol compounds of this type include PEPCD NT2006 (a polycarbonate diol compound having a tetramethylene glycol structure as an alkylene glycol structure, liquid (transparent) at 25°C, number average molecular weight 2000, glass transition temperature -84°C, manufactured by Mitsubishi Chemical Corporation), PEPCD NT2002 (a polycarbonate diol compound having a tetramethylene glycol structure as an alkylene glycol structure, liquid (transparent) at 25°C, number average molecular weight 2000, glass transition temperature -71°C, manufactured by Mitsubishi Chemical Corporation), PTMG 2000 (polytetramethylene ether glycol, number average molecular weight: 2000, manufactured by Mitsubishi Chemical Corporation), and PTMG 3000 (polytetramethylene ether glycol, number average molecular weight: 3000, manufactured by Mitsubishi Chemical Corporation).

[0076] The content of the alcohol compound (E) 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, and even more preferably 5% by mass or more. Also, is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0077] Other ingredients (F) The epoxy resin composition described above may or may not contain components other than the epoxy resin (A), curing accelerator (B), inorganic filler (C), curing agent (D), and alcohol compound (E) (hereinafter referred to as "other components (F)"). Other components (F) include, for example, curable compounds other than epoxy resin (A), such as (meth)acrylate compounds, maleimide compounds, oxetane compounds, and polysiloxane compounds; thermoplastic resins such as polyethylene resins, polyester resins, polyurethane resins, and polyamide resins; elastomers such as glycidyl group-containing acrylic resins, cyanate esters, fluororesins, phenoxy resins, benzoxazine compounds, polyimides, organotitanium compounds, phosphate esters, polyester polyols, silicone compounds, polybutadiene compounds, acrylonitrile-butadiene copolymers, and acrylic block copolymers; coupling agents; core-shell rubber particles; silicone additives (silicone oil); surfactants (e.g., silicone surfactants such as polyether-modified polydimethylsiloxane); ion trapping agents; leveling agents; antioxidants; defoaming agents; flame retardants; colorants such as carbon black; reactive diluents; photopolymerization initiators; acid generators; dispersants; release agents; fluxes; and solvents. Other components (F) can be used individually or in combination of two or more.

[0078] Examples of the coupling agents mentioned above include silane coupling agents such as vinyl, glycidoxy, (meth)acrylic, amino, mercapto, or imidazole types; titanium coupling agents such as alkoxide, chelate, or acylate types; and various other coupling agents such as long-chain spacer type coupling agents such as glycidoxyoctyltrimethoxysilane or methacrylooctyltrimethoxysilane. Examples of the silane coupling agents mentioned above include 3-isocyanatetopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

[0079] Examples of the above-mentioned elastomers include butadiene-based elastomers, silicone-based elastomers, acrylic copolymers, and styrene-butadiene-based elastomers. The above-mentioned elastomer may also be a core-shell rubber particle. That is, it may be a core-shell rubber type elastomer. A core-shell rubber particle means a rubber particle composed of a core portion and one or more shell layers covering the core portion.

[0080] The content of other components (F) 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 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. Also, for example, it may be 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more.

[0081] From the viewpoint of suppressing the generation of voids in the cured product, the solvent content in the above epoxy resin composition (100% by mass) is preferably, for example, 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less.

[0082] (Physical properties and manufacturing method of epoxy resin composition) The viscosity of the epoxy resin composition at 25°C is not particularly limited, but is preferably 1 to 1000 Pa·s, more preferably 10 to 800 Pa·s, even more preferably 30 to 600 Pa·s, even more preferably 35 to 500 Pa·s, and particularly preferably 100 to 500 Pa·s. When the viscosity is within the above range, the gap-filling ability and workability of the epoxy resin composition are improved, and the warping of the wafer after molding tends to be reduced. The viscosity can be measured using a Brookfield viscometer (model: HB-DV1, manufactured by Brookfield Corporation) at a liquid temperature of 25°C, rotated at 10 rpm for 1 minute, as shown in the examples described later.

[0083] The viscosity of the epoxy resin composition at 120°C is not particularly limited, but is preferably 0.1 Pa·s or higher, and more preferably 0.3 Pa·s or higher. Also, for example, 10 Pa·s or lower is preferred. The viscosity of the epoxy resin composition at 120°C can be measured using a MARS rheometer (rotational rheometer) manufactured by HAAKE, by applying a vibration of 10 Hz to the epoxy resin composition for 40 seconds at 120°C in oscillation strain control mode.

[0084] The thixotropic index (TI) value of the epoxy resin composition described above is not particularly limited, but is preferably 0.05 or higher, more preferably 0.1 or higher, even more preferably 0.13 or higher, and particularly preferably 0.16 or higher. Alternatively, it is preferably 1.2 or lower, more preferably 0.8 or lower, even more preferably 0.5 or lower, and particularly preferably 0.3 or lower. The thixotropic index (TI) value can be calculated as the ratio of the viscosity at 1 rpm to the viscosity at 10 rpm.

[0085] The gel time of the epoxy resin composition described above is not particularly limited, but is preferably 200 seconds or more, more preferably 300 seconds or more, and even more preferably 400 seconds or more. Alternatively, it is preferably 1000 seconds or less, more preferably 800 seconds or less, and even more preferably 600 seconds or less. The gel time of the epoxy resin composition described above can be measured using the automated curing time measuring device "MADOKA" (model number: MDK023) and stirring rod (model number: 5TC-72890) manufactured by Cyber ​​Co., Ltd., under the conditions of a sample volume of 0.3 ml, rotation of 120 rpm, revolution of 50 rpm, gap of 0.3 mm, and test temperature of 120°C.

[0086] 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 accelerator (B), inorganic filler (C), and at least one selected from the group consisting of a curing agent (D), alcohol compound (E), and other components (F) 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 a curing agent (D) to prepare the epoxy resin composition.

[0087] 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.

[0088] The epoxy resin composition described above can be preferably used as a material (epoxy resin composition for semiconductor encapsulation) for encapsulating materials placed (mounted) on a support such as semiconductor elements, wiring, and solder (solder bumps) in a semiconductor device. By using the epoxy resin composition described above as an epoxy resin composition for semiconductor encapsulation, highly reliable semiconductor devices can be manufactured. Furthermore, the epoxy resin composition described above can be preferably used as a material (epoxy resin composition for flip-chip semiconductor encapsulation) for encapsulating semiconductor elements placed (mounted) on a support in a flip-chip type semiconductor device. Specifically, by filling the gap between the semiconductor element and the support (e.g., a substrate) with the epoxy resin composition and heat-curing it, the material connecting the semiconductor element and the support (e.g., solder bumps) is encapsulated, while the semiconductor element and the support are bonded and fixed together as an encapsulant, thereby improving the reliability of the semiconductor device and reducing the occurrence of connection failures of the material (e.g., solder bumps). In particular, in high-density packaging such as 2.5D stacking technology and 3D stacking technology, heat tends to build up in the semiconductor device as a whole due to the stacking of multiple semiconductor elements (e.g., semiconductor chips), interposers, substrates, and other support structures. The epoxy resin composition of the present invention provides a cured product that combines excellent reflow resistance and heat dissipation properties, making it suitable for use in the above-mentioned applications.

[0089] Furthermore, in 2.5-dimensional stacking technology, the epoxy resin composition is used to seal the gap formed between the semiconductor element (e.g., a semiconductor chip), an interposer, and a substrate in a semiconductor device comprising a laminate in which these elements are stacked in that order. In 3-dimensional stacking technology, the epoxy resin composition is used to seal the gap formed between the semiconductor element and the other semiconductor element, and / or the gap formed between the other semiconductor element and the substrate, in a semiconductor device comprising a plurality of semiconductor elements and a substrate, wherein one of the plurality of semiconductor elements is stacked in the order of one semiconductor element, another semiconductor element, and the substrate.

[0090] The epoxy resin composition described above may be liquid or solid at room temperature (25°C), but it is preferably liquid. Furthermore, the epoxy resin composition can be used, for example, as underfill such as capillary underfill, liquid mold underfill, secondary underfill, and pre-filled underfill, as well as as a grab-top material and a liquid compression molding material. Among these uses, the epoxy resin composition is preferred when used as a liquid compression molding material because it fully exhibits the characteristic of suppressing wafer warping after molding. Moreover, the epoxy resin composition is not limited to its use as a semiconductor encapsulating epoxy resin composition as described above; for example, it can be used as an adhesive for fixing, joining, or protecting components that constitute electronic components.

[0091] <Cured product> A cured product is formed by curing the above epoxy resin composition. The curing method is not particularly limited. For example, it can be carried out by subjecting the epoxy resin composition to a heat treatment. The heat treatment temperature is not particularly limited. For example, 60 to 200 °C is preferred, and 80 to 180 °C is more preferred. The time of the heat treatment is not particularly limited. For example, 0.1 to 5 hours is preferred, and 0.5 to 3 hours is more preferred. The pressure of the heat treatment is not particularly limited. For example, 100 to 800 kN is preferred, and 170 to 750 kN is more preferred.

[0092] The fracture toughness K1c (Mpa·m 1 / 2 ) of the cured product obtained by heat-curing the above epoxy resin composition under the conditions of 150 °C for 1 hour at 25 °C is not particularly limited. For example, it is preferably 1 Mpa·m 1 / 2 or more, more preferably 1.2 Mpa·m 1 / 2 or more, still more preferably 1.4 Mpa·m 1 / 2 or more, particularly preferably 1.5 Mpa·m 1 / 2 or more. Also, for example, it is preferably 5 Mpa·m 1 / 2 or less, more preferably 4 Mpa·m 1 / 2 or less, still more preferably 3 Mpa·m 1 / 2 or less. When the fracture toughness K1c is within the above range, the occurrence of cracks tends to be reduced. The fracture toughness K1c (Mpa·m 1 / 2 ) can be measured by the method described in the examples below.

[0093] In the epoxy resin composition described above, the glass transition temperature (Tg) of the cured product is not particularly limited, but is preferably 110°C or higher, more preferably 115°C or higher, even more preferably 120°C or higher, and particularly preferably 130°C or higher. Alternatively, it is preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 165°C or lower. Having the glass transition temperature within this range improves reliability. Similarly, in the epoxy resin composition described above, the glass transition temperature (Tg) of the cured product is preferably 110 to 180°C, more preferably 115 to 170°C, even more preferably 120 to 165°C, and even more preferably 130 to 165°C. The glass transition temperature can be measured using a dynamic viscoelastic device to measure the storage modulus (E') and loss modulus (E'') of the cured epoxy resin composition, and the peak value of tanδ, which is the ratio of these two values, is taken as the glass transition temperature (Tg). The above measurement conforms to the Japanese Industrial Standard JIS C6481. The above cured product is obtained by curing it at 180°C for 60 minutes.

[0094] The storage modulus (GPa) at 30°C of the cured product obtained by heating and curing the above epoxy resin composition at 150°C for 60 minutes is not particularly limited, but is preferably 4 GPa or more, more preferably 6 GPa or more, even more preferably 8 GPa or more, even more preferably 10 GPa or more, and particularly preferably 12 GPa or more. Alternatively, it is preferably 25 GPa or less, more preferably 22 GPa or less, even more preferably 20 GPa or less, and particularly preferably 18 GPa or less. When the storage modulus is within the above range, the occurrence of cracks tends to be reduced. The storage modulus (GPa) can be measured by the method described in the examples below.

[0095] The storage modulus (GPa) at 245°C of the cured product obtained by heat-curing the above epoxy resin composition at 150°C for 60 minutes is not particularly limited, but is preferably 0.5 GPa or higher, more preferably 1 GPa or higher, even more preferably 1.5 GPa or higher, and particularly preferably 2 GPa or higher. Alternatively, it is preferably 6 GPa or lower, more preferably 5 GPa or lower, even more preferably 4 GPa or lower, and particularly preferably 3.5 GPa or lower. When the storage modulus is within the above range, the occurrence of cracks tends to be reduced. The storage modulus (GPa) can be measured by changing the measurement temperature to 245°C in the method for measuring the storage modulus (GPa) at 30°C.

[0096] The coefficient of linear expansion (CTE1) (ppm / °C) of the cured product obtained by heating and curing the above epoxy resin composition at 165°C for 120 minutes is not particularly limited, but is preferably 0 ppm / °C or higher, more preferably 5 ppm / °C or higher, even more preferably 10 ppm / °C or higher, and particularly preferably 13 ppm / °C or higher. Also, is preferably 30 ppm / °C or lower, more preferably 25 ppm / °C or lower, and even more preferably 20 ppm / °C or lower. When the coefficient of linear expansion is within the above range, the occurrence of cracks caused by temperature changes tends to be reduced. The coefficient of linear expansion (CTE1) can be measured by thermomechanical analysis (TMA) using a TMA4000SA (manufactured by Bruker).

[0097] The coefficient of linear expansion (CTE2) (ppm / °C) of the cured product obtained by heating and curing the above epoxy resin composition at 165°C for 120 minutes is not particularly limited, but is preferably 10 ppm / °C or higher, more preferably 15 ppm / °C or higher, even more preferably 20 ppm / °C or higher, and particularly preferably 25 ppm / °C or higher. Alternatively, it is preferably 60 ppm / °C or lower, more preferably 50 ppm / °C or lower, and even more preferably 40 ppm / °C or lower. When the coefficient of linear expansion is within the above range, the occurrence of cracks caused by temperature changes tends to be reduced. The coefficient of linear expansion (CTE2) can be measured by thermomechanical analysis (TMA) using a TMA4000SA (manufactured by Bruker).

[0098] <Semiconductor device and method for manufacturing the same> The semiconductor device of the present invention comprises a support, a semiconductor element mounted on the support, and a cured product of the epoxy resin composition that seals the gap formed by the support and 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 support and the semiconductor element are connected via bump electrodes. Furthermore, in the semiconductor device, the gap between the semiconductor element and the support is sealed by the cured product (sealant) of the epoxy resin composition.

[0099] The method for manufacturing a semiconductor device of the present invention is: A step of supplying the epoxy resin composition to a laminate comprising a support and a semiconductor element mounted on the support (hereinafter referred to as the "composition supply step"), The process involves filling the gap between the support and the semiconductor element with the epoxy resin composition, and then curing it to seal the semiconductor element and obtain a sealed body (hereinafter referred to as the "sealing process"), It is characterized by including.

[0100] The semiconductor device manufacturing method of the present invention may further include a step of polishing the above-mentioned encapsulant (hereinafter referred to as the "grinding step"). It may also include at least one step selected from the group consisting of the laminate preparation step and the individualization step described later.

[0101] (Laminate preparation process) The laminate preparation step is a step of preparing a laminate comprising a support and semiconductor elements mounted on the support by mounting semiconductor elements on the support. Examples of semiconductor elements include semiconductor chips. In the laminate, the support and the semiconductor elements may be connected via solder (solder bumps), or via adhesive films such as die attach films (DAF) or adhesive sheets. They may also be connected via through-silicon vias (TSVs). The support is not particularly limited, but examples include silicon wafers, silicon carbide wafers, sapphire wafers, compound semiconductor wafers (gallium phosphide, gallium arsenide, indium phosphide, gallium nitride), glass epoxy substrates, organic substrates (FR4 substrates), etc. The support also includes interposers used in 2.5-dimensional stacking technology for semiconductor devices. The shape of the support in plan view is not particularly limited, but examples include circular or rectangular shapes.

[0102] The laminate prepared in the laminate preparation process may be a laminate used in semiconductor devices that utilize 2.5-dimensional stacking technology or 3-dimensional stacking technology.

[0103] (Composition supply process) The composition supply step is a step of supplying the epoxy resin composition to a laminate comprising a support and a semiconductor element mounted on the support.

[0104] In this process, the supplied epoxy resin composition may be heated to increase its fluidity and improve its ability to fill gaps. The heating temperature is not particularly limited, but is, for example, 40 to 120°C.

[0105] In this process, the method of supplying the epoxy resin composition to the laminate is not particularly limited, but examples include coating or dropping it onto the laminate using a dispenser. Examples of the areas to which the epoxy resin composition is supplied include the top surface of the laminate (top surface of the semiconductor element) and the edges of the semiconductor element.

[0106] In the sealing step, if a molded body is formed (i.e., if the epoxy resin composition of the present invention is used as the LCM material), this step may include a step of attaching a mold used for forming the molded body to the laminate. That is, the composition supply step may be a step of supplying the epoxy resin composition to a laminate comprising a support and a semiconductor element mounted on the support, and then attaching a mold to the laminate.

[0107] Furthermore, if the molding process involves forming a molded body in the sealing process, this process may involve supplying the epoxy resin composition to a mold used for forming the molded body, and then mounting a laminate comprising a support and a semiconductor element mounted on the support into the mold. By performing such a process, the epoxy resin composition can be supplied to the laminate comprising the support and the semiconductor element mounted on the support.

[0108] (Sealing process) The sealing step involves filling the gap between the support and the semiconductor element with the epoxy resin composition, and then curing it to seal the semiconductor element and obtain a sealed body.

[0109] When the epoxy resin composition of the present invention is used as an underfill material, the epoxy resin composition is supplied to the end of the semiconductor element, causing it to spontaneously flow into the gap between the support and the semiconductor element by capillary action, thereby completing the filling. By curing the laminate after filling is complete, a encapsulated semiconductor element is obtained. This process may include a step for encapsulating the entire semiconductor element after sealing the gap. That is, this process may include two steps: (1) a step of sealing the gap between the support and the semiconductor element by filling the gap with the epoxy resin composition and curing it (gap sealing step), and (2) a step of applying an encapsulant to the laminate obtained after the gap sealing step so as to cover the semiconductor element, and further curing it to obtain a encapsulated element (overmolding step). The encapsulant used in the overmolding step may be the epoxy resin composition of the present invention or another epoxy resin composition. Furthermore, this process may include a step for encapsulating the entire semiconductor element simultaneously with sealing the gap.

[0110] In semiconductor devices using 2.5D stacking technology, a gap is also formed between the interposer and the substrate on which the interposer is mounted. In this case, the process may include a step of filling the gap between the interposer and the substrate with a sealing material and then curing it to seal the gap. This step may be performed before step (1) above, or simultaneously with step (1) above. It may also be performed between step (1) and step (2) above, or after step (2) above. The sealing material used in the above step may be the epoxy resin composition of the present invention or another epoxy resin composition.

[0111] Furthermore, in semiconductor devices to which three-dimensional stacking technology is applied, a gap is also formed between one semiconductor element and another semiconductor element stacked with that one semiconductor element. In this case, in this step, simultaneously with step (1) above, the epoxy resin composition of the present invention may be used to fill the gap between the one semiconductor element and the other semiconductor element, and the gap may be sealed by subsequent curing. That is, step (1) above may be a step in which the epoxy resin composition is used to fill the gap between the support and the semiconductor element, and the gap between the one semiconductor element and the other semiconductor element, and then cured to seal the two gaps.

[0112] When the epoxy resin composition of the present invention is used as an LCM material, this step may be a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a seal. In this case, this step may include two steps: a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body (molding step), and a step of curing the molded body obtained in the molding step to seal the semiconductor element and obtain a seal (sealing step).

[0113] The method for forming the molded body is not particularly limited, but for example, one method involves pushing a mold attached to the laminate in the direction of the laminate (support), and, if necessary, reducing the pressure inside the mold to fill the gap between the support and the semiconductor element with the epoxy resin composition, thereby forming a compression molded body containing the laminate and the epoxy resin composition. In this step, instead of pushing the mold in the direction of the laminate (support), the laminate (support) may be pushed in the direction of the mold, or a configuration in which the mold and the laminate (support) are squeezed together may be adopted.

[0114] One method for forming a molded body is to use a molding apparatus to reduce the viscosity of an epoxy resin composition by heating as needed, and then reduce the pressure of the epoxy resin composition to seal the laminate. A molded body can be obtained by this forming method.

[0115] In this process, the epoxy resin composition may be cured by heating. The curing temperature is not particularly limited, but is preferably 110 to 200°C, and more preferably 120 to 150°C. The curing time is not particularly limited, but is preferably 30 minutes to 7 hours, more preferably 1 to 6 hours, even more preferably 1 to 4 hours, and particularly preferably 1 to 2 hours.

[0116] (polishing process) The polishing process involves polishing the encapsulated body obtained in the sealing process. More specifically, it involves polishing the surface of the encapsulated body on the semiconductor element side in order to flatten and thin the encapsulated body, and exposing a portion of the semiconductor element as needed. The polishing method is not particularly limited, and commercially available polishing wheels and polishing equipment can be used.

[0117] (Singulation process) The individualization step is a process of separating the sealed body obtained in the sealing step or the sealed body polished in the polishing step into individual pieces. The individualization step may also be a process of separating the sealed body after removing it from the mold. In the individualization step, the gaps between multiple semiconductor elements mounted on the support and sealed with a cured epoxy resin composition are cut using means such as a dicing blade or a laser to obtain a semiconductor device. The method of individualization is not particularly limited, and commercially available individualization devices can be used.

[0118] In this specification, the term "semiconductor device" refers not only to semiconductor elements, semiconductor elements mounted on a support (substrate), and semiconductor elements connected to each other, but also to all devices that can function by utilizing the properties of semiconductor elements. Such semiconductor devices may include electronic components other than semiconductor elements, such as resistors, coils, capacitors, and transformers.

[0119] The following describes embodiments of a semiconductor device manufacturing method using Figures 1 and 2, but the present invention is not limited thereto.

[0120] Figure 1 shows one embodiment of the method for manufacturing a semiconductor device according to the present invention. This embodiment will be described below with reference to Figure 1. A semiconductor element 1, having solder bumps 2 on one side, is mounted on a support 3, and a laminate 4 is prepared containing the semiconductor element 1, solder bumps 2, and support 3 in this order (laminated laminate preparation step, (a)). An epoxy resin composition 5 is supplied onto the semiconductor element 1 of the laminate 4 using a syringe 6, and then a mold 7 is attached (composition supply step, (b) and (c)). In this step, a release film may be provided on the surface of the mold 7 that is oriented toward the laminate 4. The release film is positioned so that the mold 7 and the epoxy resin composition 5 do not come into contact, and also to facilitate the removal of the sealant 9 from the mold 7 in step (f) described later. The release film is not shown in the figure. PET film or PE film can be used as the release film. The thickness of the release film is, for example, 30 to 100 μm. The release film may have a release treatment or a matte finish applied to at least one of its surfaces. Specific examples of release films include "50HK" (thickness 50 μm) and "50MW" (thickness 50 μm) from AGC Inc.; "TBM" (thickness 70 μm) from TOWA Corporation; "MintRow AEH50-2S" (thickness 50 μm) from Mitsui Chemicals ICT Materia Co., Ltd.; "PJ271" (thickness 50 μm) from Toray Industries, Inc.; and "RM-4100" from Resona Co., Ltd. Next, the mounted mold 7 is pushed in the direction of the support 3, and the pressure inside the mold 7 is reduced as needed to form a compression molded body 8 containing the laminate 4 and the epoxy resin composition 5 (molding process, (d)). In this process, instead of pushing the mold 7 in the direction of the support 3, the support 3 may be pushed in the direction of the mold 7, or a manner in which the mold 7 and the support 3 are narrowed relative to each other may be adopted. In this process, the epoxy resin composition 5 is filled into the gap between the support 3 and the semiconductor element 1, forming the compression molded body 8. The compression molded body 8 is heat-cured to enclose the semiconductor element 1, thereby forming a encapsulated body 9 (encapsulation step, (e)). After removing the mold 7, the encapsulated body 9 containing the semiconductor element 1 is separated into individual pieces (separation steps, (f) and (g)).

[0121] Figure 2 shows another embodiment of the semiconductor device manufacturing method of the present invention. This embodiment will be described below with reference to Figure 2. A semiconductor element 11, having solder bumps 12 on one side, is mounted on a support 13, and a laminate 14 is prepared containing the semiconductor element 11, solder bumps 12, and support 13 in this order (laminated laminate preparation step, (a)). After supplying the epoxy resin composition 15 to the mold 17 using a syringe 16, the laminate 14 is mounted in the mold (composition supply step, (b) and (c)). In this step, a release film may be provided on the supply surface of the epoxy resin composition 15 in the mold 17. That is, in this step, (1) the epoxy resin composition 15 may be supplied to the surface of the mold 17 that has the release film, or (2) the epoxy resin composition 15 may be supplied onto the release film, and then the release film may be placed in the mold 17. The release film is positioned so that the mold 17 and the epoxy resin composition 15 do not come into contact, and also to facilitate the removal of the sealant 19 from the mold 17 in step (f) described later. The release film is not shown in the figure. Next, the inside of the mold 17 is depressurized to form a compression molded body 18 containing the laminate 14 and the epoxy resin composition 15 (molding step, (d)). In this step, the epoxy resin composition 15 is filled into the gap between the support 13 and the semiconductor element 11, forming the compression molded body 18. The compression molded body 18 is heat-cured to seal the semiconductor element 11, forming a sealant 19 (sealing step, (e)). After removing the mold 17, the sealant 19 containing the semiconductor element is separated into individual pieces (separation steps, (f) and (g)).

[0122] Note that while Figures 1 and 2 show the semiconductor element as a single-layer structure for illustrative purposes, it may also have a multilayer structure as shown in Figures 4 and 5.

[0123] Figure 4 shows an embodiment of the semiconductor device of the present invention that applies 2.5-dimensional stacking technology. This embodiment will be described below in reference to Figure 4. The semiconductor device 20 comprises a semiconductor element (semiconductor chip) 21, solder bumps 22, a encapsulant 23, through-electrodes 24, an interposer 25, solder bumps 26, a substrate 27, solder bumps 28, and a package substrate 29. The semiconductor device 20 is a semiconductor device in which the semiconductor element 21 is mounted in 2.5 dimensions, and has a structure in which a plurality of semiconductor elements 21 are arranged on the interposer 25. The through-electrodes 24 are electrodes that penetrate the interposer 25 in the thickness direction. The encapsulant 23 is a cured product of the epoxy resin composition of the present invention. The semiconductor element 21, the interposer 25, and the substrate 27 are stacked in this order to form a laminate. The semiconductor device 20 has a structure in which the electrode portion of the semiconductor element 21 is connected to the electrode portion on the interposer 25 via the solder bumps 22, and further connected to the electrode portion on the interposer 25 and the electrode portion on the substrate 27.

[0124] In this embodiment, the epoxy resin composition of the present invention is used as an epoxy resin composition for sealing the gap formed between the semiconductor element and the interposer in a semiconductor device comprising a laminate in which a semiconductor element, an interposer, and a substrate are stacked in that order. Preferably, the pitch of the bumps disposed between the semiconductor element and the interposer is 50 μm or less. The epoxy resin composition of the present invention provides a cured product that has high filling properties even when the bump pitch is 50 μm or less, and also possesses excellent reflow resistance and heat dissipation properties.

[0125] Furthermore, in this embodiment, the semiconductor device of the present invention is a semiconductor device comprising a laminate in which semiconductor elements, an interposer, and a substrate are stacked in this order, and further comprising a cured product that seals the gap formed by the semiconductor elements and the interposer.

[0126] Figure 5 shows an embodiment of the semiconductor device of the present invention that applies three-dimensional stacking technology. This embodiment will be described below with reference to Figure 5. The semiconductor device 30 comprises a semiconductor element 31, solder bumps 32, a encapsulant 33, a through-electrode 34, a substrate 35, and a package substrate 36. The semiconductor device 30 is a semiconductor device in which the semiconductor element 31 is mounted in three dimensions and has a multilayer structure. The through-electrode 34 is an electrode that penetrates the semiconductor element 31 in the thickness direction. The encapsulant 33 is a cured product of the epoxy resin composition of the present invention.

[0127] In this embodiment, the epoxy resin composition of the present invention is used as an epoxy resin composition for sealing gaps formed by multiple semiconductor elements and gaps formed between the semiconductor elements and the substrate in a semiconductor device comprising a laminate in which multiple (two or more) semiconductor elements and a substrate are stacked in that order. The epoxy resin composition of the present invention provides a cured product that has high filling properties even when multiple semiconductor elements and substrates are stacked at high density, and also possesses excellent reflow resistance and heat dissipation properties.

[0128] Furthermore, in this embodiment, the semiconductor device of the present invention is a semiconductor device comprising a plurality of semiconductor elements and a substrate, wherein the semiconductor device comprises a laminate in which one semiconductor element from the plurality of semiconductor elements, other semiconductor elements from the plurality of semiconductor elements, and the substrate are stacked in this order, and comprises a cured product that seals the gap formed by the one semiconductor element and the other semiconductor elements, and / or the gap formed by the other semiconductor elements and the substrate. The other semiconductor elements may be one or two or more. [Examples]

[0129] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0130] The epoxy resin compositions of the examples and comparative examples were prepared by mixing each component in the proportions shown in Table 1. Note that the values ​​for each component in Table 1 represent parts by mass.

[0131] The following is a description of each component in Table 1. (Epoxy resin (A)) • Epoxy resin (A1) EP-4005 (Product name: ADEKA Resin EP-4005): A bisphenol A type epoxy resin containing a polypropylene glycol structure, represented by formula (4), with m+n = 10, epoxy equivalent weight 510 g / eq, liquid at 25°C, manufactured by ADEKA Corporation. EP-4003S (Product name: ADEKA Resin EP-4003S): A bisphenol A type epoxy resin containing a polypropylene glycol structure, represented by formula (4), with m+n being 4, epoxy equivalent weight 470 g / eq, liquid at 25°C, manufactured by ADEKA Corporation. AER-9000 (product name): PO-modified bisphenol type epoxy resin, represented by formula (4), with m+n = 5, epoxy equivalent weight 380 g / eq, liquid at 25°C, manufactured by Asahi Kasei Corporation. EX-171 (product name): Represented by formula (3), R is an alkyl group with 12 carbon atoms, l is a 15-carbon epoxy resin, epoxy equivalent weight 971 g / eq, liquid at 25°C, manufactured by Nagase ChemteX Corporation. • Epoxy resin (A2) YDF8170 (Product Name): Bisphenol F type epoxy resin, epoxy equivalent 155-165 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. jER630 (product name): Aminophenol-type epoxy resin, 3 epoxy groups, epoxy equivalent weight 90-106 g / eq, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation. EP3980S (Product Name): Glycidylamine type epoxy resin, 2 epoxy groups, epoxy equivalent weight 135 g / eq, liquid at 25°C, manufactured by ADEKA Corporation. YX7400N (Product Name): Aliphatic epoxy resin (difunctional long-chain aliphatic glycidyl ether), epoxy equivalent 440 g / eq, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation. X-40-2669 (Product Name): Difunctional linear siloxane oligomer containing alicyclic epoxy groups, manufactured by Shin-Etsu Chemical Co., Ltd. (Curing accelerator (B)) 2MZA-PW (Product Name): 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, manufactured by Shikoku Chemicals Co., Ltd. 2P4MZ (Product Name): 2-phenyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd. 2E4MZ-CN (Product Name): 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd. CG1400: Product name is AMICURE CG1400, dicyandiamide, manufactured by Evonik Japan Co., Ltd. (Inorganic filler (C)) SE605H-SMG (Product Name): Silicon dioxide surface treated with 3-methacryloxypropyltrimethoxysilane, average particle size 1.8 μm, manufactured by Admatex Co., Ltd. SE101G-SMO (Product Name): Silicon dioxide surface treated with 3-methacryloxypropyltrimethoxysilane, average particle size 0.2 μm, manufactured by Admatex Co., Ltd. YA050C-SM1 (Product Name): Silicon dioxide surface treated with 3-methacryloxypropyltrimethoxysilane, average particle size 0.05 μm, manufactured by Admatex Co., Ltd. (Hardening agent (D)) MEH-8005 (Product Name): Phenolic curing agent (allylated phenol novolac resin), hydroxyl group equivalent 139-143 g / eq, manufactured by Meiwa Chemical Industries, Ltd. (Other ingredients (F)) KBM-803 (Product Name): 3-Mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

[0132] (Evaluation 1: Measurement of warping) On a circular silicon wafer with a diameter of 300 mm and a thickness of 775 μm, the epoxy resin compositions of the examples and comparative examples were applied to a thickness of 100 μm and 500 μm, respectively, using a molding apparatus (Apic Yamada Co., Ltd., WCM-300). The substrates coated with the epoxy resin compositions were molded at 150°C, with a mold cure time of 300 seconds and a clamping force of 250 kN, followed by post-mold curing (PMC) at 150°C for 1 hour. After the resulting encapsulated material was allowed to stand for 1 hour immediately after PMC, the amount of warpage at 25°C was measured using a shadow moiré apparatus (Akrometrix, AXP 2.0-DFP2). The highest point was recorded when the cured material surface was placed on a horizontal table. The results are shown in Table 1. In Table 1, "Warpage 1 (μm)" is used to represent the warpage when the epoxy resin composition has a thickness of 100 μm, and "Warpage 2 (μm)" is used to represent the warpage when the epoxy resin composition has a thickness of 500 μm.

[0133] In Evaluation 1, if the "warpage" of the epoxy resin composition with a thickness of 100 μm, i.e., "warpage 1 (μm)", is 1500 μm or less, the warpage of the molded wafer can be evaluated as small. Also, if the "warpage" of the epoxy resin composition with a thickness of 500 μm, i.e., "warpage 2 (μm)", is 10000 μm or less, the warpage of the molded wafer can be evaluated as small.

[0134] (Evaluation 2: Measurement of storage modulus at 30°C) The epoxy resin compositions of the examples and comparative examples were heated and cured at 150°C for 60 minutes to produce cured products. The storage modulus (GPa) at 30°C of the obtained cured products was measured by DMA (Dynamic Mechanical Analysis) using a DMS7100 from SII. The results are shown in Table 1 under "Storage Modulus at 30°C (GPa)".

[0135] (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 HB-DV viscometer (model number: HB-DV1). The viscosity was measured when the epoxy resin compositions were rotated at 10 rpm for 1 minute at a liquid temperature of 25°C. For this measurement, the epoxy resin compositions used were those prepared immediately. The results are shown in Table 1 under "Viscosity at 25°C (Pa·s)".

[0136] (Evaluation 4: Measurement of durability / fracture toughness (K) IC )) The cured products of the epoxy resin compositions of the examples and comparative examples were subjected to fracture toughness (K) in accordance with ASTM D5045-99. IC ) was measured. An epoxy resin composition was heat-cured at 150°C for 1 hour to prepare a test specimen measuring 75 mm in length, 14 mm in width, and 7 mm in thickness. Using the obtained test specimen, the fracture toughness value (K1c) (MPa·m) at 25°C was measured using a Shimadzu Autograph AG-IS (manufactured by Shimadzu Corporation). 1 / 2 The fracture toughness K1c (MPa·m) was measured. The distance between supports during measurement was 56 mm, and the pre-crack depth was 7.4-8.3 mm. The results are shown in Table 1. 1 / 2 ) will be included in the description.

[0137] (Rating 5: Delamination rating) A component was prepared consisting of a circular silicon wafer with a diameter of 12 inches and a thickness of 760 μm, on which four silicon chips measuring 18 mm in length, 18 mm in width, and 300 μm in thickness (height) were mounted. The silicon chips were mounted circumferentially at equal intervals (every 90°) along the vicinity of the outer edge of the silicon wafer. The silicon chips were mounted onto the silicon wafer by first placing (applying) spacers to the surface of the silicon chips, and then attaching the spacer-placed surface of the silicon chips to the silicon wafer surface. A total of nine spacers were placed on the surface of the silicon chips in an X-shape at equal intervals. The height of the spacers was set to 20 μm. Next, the epoxy resin compositions of the example and comparative example were filled into a mold, and the above component was placed and the mold was pressed to perform compression molding. As a result, the silicon chips placed on the silicon wafer were sealed by the epoxy resin composition, forming a sealing layer (cured epoxy resin layer) with a thickness of 500 μm, and a molded product was obtained. Next, the molded product was removed from the mold, and a cut piece was obtained by cutting the area including the silicon chip and its vicinity. Furthermore, this cut piece was cut so that the cross-section of the central part of the silicon chip was exposed to obtain an evaluation sample. The area near the silicon chip on the cross-section of the evaluation sample was observed using a scanning electron microscope (magnification: 1500x) to check for delamination at the interface between the encapsulation layer and the silicon chip. Samples without delamination were marked with "○" and those with delamination were marked with "×", and the results are recorded in Table 1 under "Delamination". Epoxy resin compositions without delamination can be judged to have excellent reliability. Figure 3 is a photograph of this evaluation in Comparative Example 1, where the silicon chip is on the left, the encapsulation layer is on the right, and the dark gray area in the center is where delamination occurred.

[0138] [Table 1]

[0139] The following describes variations of the invention relating to this disclosure. [Note 1] An epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), An epoxy resin composition comprising epoxy resin (A1), which has a glycidyl ether group and a polyethylene glycol group and / or a polypropylene glycol group, as epoxy resin (A). [Note 2] The epoxy resin composition according to [Appendix 1], wherein the content of epoxy resin having three or more epoxy groups is 60% by mass or less relative to epoxy resin (A) (100% by mass). [Note 3] The epoxy resin composition according to [Appendix 1] or [Appendix 2], wherein the liquid epoxy resin content is 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, relative to epoxy resin (A) (100% by mass). [Note 4] The epoxy resin (A1) is an epoxy resin having two or three glycidyl ether groups, as described in any one of [Appendix 1] to [Appendix 3]. [Note 5] Epoxy resin (A1) is given by formula (1) [ka] (In the formula, R represents an alkyl group having 10 to 15 carbon atoms. X represents a polyethylene glycol group or a polypropylene glycol group.) The epoxy resin shown in (A1-1), or formula (2) [ka] (In the formula, Y and Z are the same or different and represent a polyethylene glycol group or a polypropylene glycol group.) The epoxy resin composition is the epoxy resin (A1-2) shown in [Appendix 1] to [Appendix 4]. [Note 6] The epoxy resin composition according to [Appendix 5], wherein the average degree of polymerization of the polyethylene glycol group or polypropylene glycol group of X is 2 to 20, 5 to 18, 8 to 16, or 10 to 15. [Note 7] The epoxy resin composition according to [Appendix 5] or [Appendix 6], wherein the average degree of polymerization of the polyethylene glycol groups or polypropylene glycol groups of Y and Z is 2 to 20, 3 to 16, and 4 to 12, respectively. [Note 8] Epoxy resin (A1) is given by formula (3) [ka] (In the formula, R represents an alkyl group with 10 to 15 carbon atoms, and l represents 10 to 20 carbon atoms.) The epoxy resin indicated by (A1-3), or formula (4) [ka] (In the formula, m represents an integer greater than or equal to 2. n represents an integer greater than or equal to 2. m+n represents an integer between 4 and 12.) The epoxy resin composition is the epoxy resin (A1-4) shown in [Appendix 1] to [Appendix 7]. [Note 9] Furthermore, the epoxy resin composition according to any one of [Appendix 1] to [Appendix 8] further comprises, as epoxy resin (A2) other than epoxy resin (A1), at least one selected from the group consisting of bisphenol-type epoxy resin (particularly bisphenol F-type epoxy resin), aminophenol-type epoxy resin, and glycidylamine-type epoxy resin. [Note 10] An epoxy resin composition that does not contain an alicyclic epoxy resin, as described in any one of [Appendix 1] to [Appendix 9]. [Note 11] The epoxy resin (A) content is 3% by mass or more, 6% by mass or more, 9% by mass or more, or 12% by mass or more, and / or 60% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 10], wherein the amount is 3-60% by mass, 6-40% by mass, 9-30% by mass, 9-25% by mass, or 12-20% by mass. [Note 12] The epoxy resin (A1) content is 0.1% by mass or more, 0.3% by mass or more, 0.6% by mass or more, 0.8% by mass or more, or 1% by mass or more, and / or 30% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 11], wherein the amount is 0.1 to 30% by mass, 0.3 to 15% by mass, 0.6 to 10% by mass, 0.8 to 8% by mass, or 1 to 6% by mass. [Note 13] The epoxy resin (A2) content is 1% by mass or more, 3% by mass or more, 6% by mass or more, 8% by mass or more, or 10% by mass or more, and / or 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 16% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 12], wherein the amount is 1-40% by mass, 3-30% by mass, 6-25% by mass, 8-20% by mass, or 10-16% by mass. [Note 14] The content of epoxy resin (A1) relative to epoxy resin (A) (100% by mass) is 1% by mass or more, 3% by mass or more, 5% by mass or more, or 6% by mass or more, and / or 80% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 30% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 13], wherein the amount is 1-80% by mass, 3-60% by mass, 5-50% by mass, 6-40% by mass, or 6-30% by mass. [Note 15] The content of epoxy resin (A1) relative to epoxy resin (A2) (100% by mass) is 1% by mass or more, 3% by mass or more, 5% by mass or more, or 6% by mass or more, and / or 80% by mass or less, 65% by mass or less, 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 14], wherein the amount is 1-80% by mass, 3-65% by mass, 5-60% by mass, 6-50% by mass, 6-45% by mass, or 6-40% by mass. [Note 16] The content of epoxy resin (A1) relative to the total amount (100% by mass) of the resin components, i.e., epoxy resin (A), curing accelerator (B), and curing agent (D), is 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass or more, and / or 50% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 15], wherein the amount is 1-50% by mass, 2-40% by mass, 3-35% by mass, 4-30% by mass, or 5-25% by mass. [Note 17] The epoxy resin composition according to any one of [Appendix 1] to [Appendix 16], comprising, as a curing accelerator (B), at least one selected from the group consisting of imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphorus-based curing accelerators, and dicyandiamide. [Note 18] The content of the curing accelerator (B) in the epoxy resin composition (100% by mass) is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.4% by mass or more, and / or 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 17], wherein the amount is 0.01 to 20% by mass, 0.05 to 15% by mass, 0.1 to 10% by mass, 0.2 to 8% by mass, 0.4 to 6% by mass, 0.4 to 4% by mass, 0.4 to 3% by mass, 0.4 to 2% by mass, or 0.4 to 1% by mass. [Note 19] In the epoxy resin composition, the content of the curing accelerator (B) relative to the epoxy resin (A) (100% by mass) is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or 2.5% by mass or more, and / or 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 18], wherein the amount is 0.1 to 60% by mass, 0.5 to 50% by mass, 1 to 40% by mass, 2 to 30% by mass, 2.5 to 20% by mass, 2.5 to 10% by mass, 2.5 to 8% by mass, or 2.5 to 6% by mass. [Note 20] The epoxy resin composition according to any one of [Appendix 1] to [Appendix 19], comprising at least one selected from the group consisting of silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, lime sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and inorganic particles whose surfaces have been treated therefrom, as the inorganic filler (C). [Note 21] The epoxy resin composition according to any one of [Appendix 1] to [Appendix 20], wherein the average particle size of the inorganic filler (C) is 1 nm to 10 μm, 5 nm to 7 μm, 10 nm to 5 μm, or 30 nm to 3 μm. [Note 22] The content of the inorganic filler (C) in the epoxy resin composition (100% by mass) is 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 74% by mass or more, and / or 90% by mass or less, 88% by mass or less, 86% by mass or less, or 85% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 21], wherein the amount is 30-90% by mass, 50-88% by mass, 60-88% by mass, 70-86% by mass, or 74-85% by mass. [Note 23] In the epoxy resin composition, the content of inorganic filler (C) relative to epoxy resin (A) (100% by mass) is 100% by mass or more, 200% by mass or more, 300% by mass or more, 350% by mass or more, or 400% by mass or more, and / or 800% by mass or less, 700% by mass or less, 650% by mass or less, 600% by mass or less, or 550% by mass or less. An epoxy resin composition as described in any one of the following [Appendix 1] to [Appendix 22], wherein the composition is 100-800% by mass, 200-700% by mass, 300-650% by mass, 350-600% by mass, or 400-550% by mass. [Note 24] The epoxy resin composition according to any one of [Appendix 1] to [Appendix 23], comprising at least one selected from the group consisting of acid anhydride-based curing agents, phenol-based curing agents, and amine-based curing agents as the curing agent (D). [Note 25] The content of the curing agent (D) in the epoxy resin composition (100% by mass) is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.5% by mass or more, and / or 5% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less. An epoxy resin composition according to any one of [Appendix 1] to [Appendix 24], wherein the amount is 0.01 to 5% by mass, 0.05 to 4% by mass, 0.1 to 3% by mass, 0.2 to 3% by mass, or 0.5 to 2% by mass. [Note 26] An epoxy resin composition according to any one of [Appendix 1] to [Appendix 25], wherein the solvent content is 1% by mass or less, 0.1% by mass or less, 0.05% by mass or less, or 0.01% by mass or less. [Note 27] An epoxy resin composition according to any one of [Appendix 1] to [Appendix 26], wherein the epoxy equivalent of epoxy resin (A1) is 300 to 1100 g / eq, 300 to 600 g / eq, or 300 to 550 g / eq. [Note 28] The fracture toughness K1c(Mpa·m) of the cured product obtained by heat-curing an epoxy resin composition at 150°C for 1 hour is determined at 25°C. 1 / 2 ) is 1 MPa·m1 / 2 More than 1.2Mpa m 1 / 2 More than 1.4Mpa m 1 / 2 Above or above, or 1.5 MPa·m 1 / 2 Above and / or 5 MPa·m 1 / 2 Below, 4Mpa m 1 / 2 Below, 3Mpa m 1 / 2 Is it the following, 1-5 MPa·m 1 / 2 , 1.2~4Mpa·m 1 / 2 , 1.4~3Mpa·m 1 / 2 , or 1.5~3Mpa·m 1 / 2 The epoxy resin composition described in any one of the following [Appendix 1] to [Appendix 27]. [Note 29] The storage modulus (GPa) at 30°C of the cured product obtained by heating and curing the epoxy resin composition at 150°C for 60 minutes is 4 GPa or more, 6 GPa or more, 8 GPa or more, 10 GPa or more, or 12 GPa or more, and / or 25 GPa or less, 22 GPa or less, 20 GPa or less, or 18 GPa or less. An epoxy resin composition according to any one of the following [Appendix 1] to [Appendix 28], having a viscosity of 4-25 GPa, 6-22 GPa, 8-20 GPa, 10-18 GPa, or 12-18 GPa. [Note 30] An epoxy resin composition described in any one of the following [Appendix 1] to [Appendix 29], which is a liquid compression molding material. [Note 31] A cured epoxy resin composition as described in any one of the following [Appendix 1] to [Appendix 30]. [Note 32] A semiconductor device comprising a cured product as described in [Appendix 31]. [Note 33] Support and A semiconductor element mounted on the aforementioned support, The cured material described in [Appendix 31] for sealing the semiconductor element, A semiconductor device equipped with a semiconductor device. [Note 34] A step of supplying an epoxy resin composition according to any one of [Appendix 1] to [Appendix 30] to a laminate comprising a support and a semiconductor element mounted on the support, The process involves filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a sealed body. A method for manufacturing a semiconductor device containing [a specific component]. [Explanation of symbols]

[0140] 1. Semiconductor element 2 solder bumps 3 Support 4 Laminate 5. Epoxy resin composition 6 Syringes 7 molds 8 Compression molded body 9 Sealing body 11 Semiconductor devices 12 solder bumps 13 Support 14 Laminate 15 Epoxy resin composition 16 Syringes 17 molds 18 Compression molded body 19 Sealing body 20 Semiconductor equipment 21. Semiconductor devices (semiconductor chips) 22 solder bumps 23 Sealing body 24 Through electrode 25 Interposer 26 solder bumps 27 circuit boards 28 solder bumps 29 Package substrates 30 Semiconductor Equipment 31. Semiconductor devices (semiconductor chips) 32 solder bumps 33 Sealing body 34 Through electrode 35 circuit boards 36 Package substrates

Claims

1. An epoxy resin composition comprising an epoxy resin (A), a curing accelerator (B), and an inorganic filler (C), An epoxy resin composition comprising epoxy resin (A1), which has a glycidyl ether group and a polyethylene glycol group and / or a polypropylene glycol group, as epoxy resin (A).

2. Epoxy resin (A1) is given by formula (1) 【Chemistry 1】 (In the formula, R represents an alkyl group having 10 to 15 carbon atoms. X represents a polyethylene glycol group or a polypropylene glycol group.) The epoxy resin shown in (A1-1), or formula (2) 【Chemistry 2】 (In the formula, Y and Z are the same or different and represent a polyethylene glycol group or a polypropylene glycol group.) The epoxy resin composition according to claim 1, wherein the epoxy resin is (A1-2) shown by [the specified symbol].

3. Epoxy resin (A1) is given by formula (3) 【Transformation 3】 (In the formula, R represents an alkyl group having 10 to 15 carbon atoms, and l is between 10 and 20 carbon atoms.) The epoxy resin shown in (A1-3), or formula (4) 【Chemistry 4】 (In the formula, m represents an integer greater than or equal to 2. n represents an integer greater than or equal to 2. m + n represents an integer between 4 and 12.) The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin is represented by (A1-4).

4. The epoxy resin composition according to claim 1 or 2, comprising an imidazole-based curing accelerator as the curing accelerator (B).

5. The epoxy resin composition according to claim 1 or 2, wherein the epoxy equivalent of the epoxy resin (A1) is 300 to 1100 g / eq.

6. The epoxy resin composition according to claim 1 or 2, wherein the content of epoxy resin (A1) relative to epoxy resin (A) (100% by mass) is 1 to 50% by mass.

7. The epoxy resin composition according to claim 1 or 2, further comprising an epoxy resin (A2) other than epoxy resin (A1) as epoxy resin (A).

8. The epoxy resin composition according to claim 7, wherein the content of epoxy resin (A1) relative to epoxy resin (A2) (100% by mass) is 1 to 65% by mass.

9. The epoxy resin composition according to claim 7, wherein the epoxy resin (A2) comprises a bisphenol-type epoxy resin.

10. The epoxy resin composition according to claim 7, wherein the epoxy resin (A2) comprises an aminophenol-type epoxy resin.

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

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

13. A semiconductor device comprising the cured product according to claim 12.

14. Support and A semiconductor element mounted on the aforementioned support, A cured product according to claim 12 for sealing the semiconductor element, A semiconductor device equipped with a semiconductor device.

15. Support and A step of supplying the epoxy resin composition according to claim 1 or 2 to a laminate comprising a semiconductor element mounted on the support, The process involves filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a sealed body. A method for manufacturing a semiconductor device containing [a specific component].

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