Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present invention relates to an epoxy resin composition, a cured product, a semiconductor device, and a method for manufacturing a semiconductor device.
• silicon interposers do not contain active elements such as transistors, they are easier to enlarge than chips. Therefore, the mainstream approach is to enlarge silicon interposers and mount more chips on them. In addition, in order to further increase the size, various interposers, such as interposers with silicon embedded in molded resin, are being considered.
• the shell layer of the core-shell rubber particles (D1) further contains at least one structural unit selected from the group consisting of methyl (meth)acrylate and glycidyl (meth)acrylate.
• the content of the core-shell rubber particles (D1) relative to the total amount (100% by mass) of the epoxy resin (A) and the curing agent (B) is preferably 1 to 30% by mass.
• the content of inorganic filler (C) relative to the epoxy resin composition (100% by mass) is preferably 50% by mass or more.
• the epoxy resin (A) preferably contains at least one selected from the group consisting of bisphenol-type epoxy resins, aminophenol-type epoxy resins, and naphthalene-type epoxy resins.
• the shell layer of the core-shell rubber particles (D1) is substantially free of styrene, acrylonitrile, and methacrylonitrile as structural units.
• the above-mentioned epoxy resin composition is preferably used for semiconductor encapsulation.
• FIGS. 1A to 1C are diagrams illustrating "Evaluation 2: Gap filling test" in the examples.
• Epoxy resin (A) The epoxy resin composition contains the epoxy resin (A), which allows it to form a cured product with high electrical insulation.
• the number of epoxy groups in the epoxy resin (A) is not particularly limited as long as it is one or more, but it is preferably two or more (i.e., a polyfunctional epoxy resin).
• the epoxy resin (A) can be used alone or in combination of two or more.
• Epoxy resin (A) may be liquid or solid at room temperature (25°C), but is preferably liquid from the viewpoint of the viscosity of the epoxy resin composition. Even solid epoxy resins can be preferably used if they are used in combination with liquid epoxy resins to form a liquid mixture.
• the content of bisphenol-type epoxy resin relative to epoxy resin (A) (100% by mass) is not particularly limited, but is preferably, for example, 0 to 100% by mass.
• the content of naphthalene-type epoxy resin relative to epoxy resin (A) (100% by mass) is not particularly limited, but is preferably, for example, 0 to 50% by mass.
• the content of aminophenol-type epoxy resin relative to epoxy resin (A) (100% by mass) is not particularly limited, but is preferably, for example, 0 to 90% by mass.
• the content of cyclohexane-type epoxy resin relative to epoxy resin (A) (100% by mass) is not particularly limited, but is preferably, for example, 0 to 30% by mass.
• liquid epoxy resins include “YDF-8170” (bisphenol F type epoxy resin), “YDF-8125” (bisphenol A type epoxy resin), “ZX-1658", and “ZX-1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "HP-4032”, “HP-4032D”, and “HP-4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation; and "jER828US”, “jER828EL” (bisphenol A type epoxy resin), “jER806", and “jER807” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation.
• Examples include “bisphenol A epoxy resin,” “jER152” (phenol novolac epoxy resin), “jER630,” “jER630LSD,” “EP3980S” (aminophenol epoxy resin), “YX7400” (high-resilience epoxy resin), “ZX1059” (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., “EX-721” (glycidyl ester epoxy resin) manufactured by Nagase ChemteX Corporation, and “Celloxide 2021P” (alicyclic epoxy resin) manufactured by Daicel Corporation.
• solid epoxy resins include DIC Corporation's "HP-4032H” (naphthalene-type epoxy resin), “HP-4700", and “HP-4710” (naphthalene-type tetrafunctional epoxy resin), “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” (dicyclopentadiene-type epoxy resin), "EXA7311", and "EXA7311-G3".
• the epoxy equivalent of the epoxy resin (A) is not particularly limited, but is preferably 30 to 1000 g/eq, more preferably 40 to 500 g/eq, and even more preferably 50 to 300 g/eq.
• the content of epoxy resin (A) relative to the above-mentioned epoxy resin composition (100% by mass) is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 12% by mass or more. It is also preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less.
• the thermal expansion of the cured product tends to be reduced and the toughness tends to be improved.
• the epoxy resin composition tends to have low viscosity and excellent injectability.
• the curing agent (B) is not particularly limited as long as it initiates, progresses, or accelerates the polymerization of the epoxy resin, and examples thereof include amine-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents.
• the curing agent (B) may be solid or liquid at room temperature (25°C), and is preferably liquid.
• the curing agent (B) may be used alone or in combination of two or more.
• the acid anhydride curing agent examples include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadic anhydride.
• the phenolic curing agent examples include phenol novolac resin, cresol novolac resin, naphthol-modified phenol resin, dicyclopentadiene-modified phenol resin, and p-xylene-modified phenol resin.
• the imidazole curing agent examples include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.
• the imidazole curing agent also include microcapsule-type imidazole curing agents. From the viewpoint of temperature cycle resistance, moisture resistance, and reliability of the semiconductor device, the curing agent (B) is preferably the above-mentioned amine-based curing agent, more preferably an aromatic amine, and even more preferably a liquid aromatic amine.
• the equivalent weight (molecular weight per functional group) of the curing agent (B) is not particularly limited, but is preferably 10 to 300 g/eq, more preferably 20 to 160 g/eq, and even more preferably 30 to 100 g/eq.
• the amount of curing agent (B) contained is not particularly limited, but it is preferably an amount that results in a stoichiometric equivalent ratio (curing agent equivalent/epoxy group equivalent) with the epoxy resin (A) of, for example, 0.5 to 1.5, and more preferably an amount that results in an equivalent ratio of 0.8 to 1.2.
• the content of curing agent (B) relative to the epoxy resin composition (100% by mass) of the present invention is not particularly limited, but is preferably, for example, 2% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more. It is also preferably, for example, 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 12% by mass or less.
• the thermal expansion of the cured product tends to be reduced and toughness tends to be improved.
• the epoxy resin composition tends to have low viscosity and excellent injectability.
• the inorganic filler (C) is not particularly limited, but is preferably (1) one having the property of suppressing volumetric shrinkage (cure shrinkage) caused by the curing reaction of the epoxy resin composition, (2) one having the property of suppressing volumetric change (thermal shrinkage) caused by heating of the cured product, i.e., one having the effect of lowering the linear expansion coefficient when added, or (3) one having both of these properties.
• inorganic fillers (C) examples 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 with their surfaces treated.
• silica is preferred from the perspective of being able to increase the loading amount, and it is more preferable to contain silica with an average particle size of 100 nm or less (sometimes referred to as "nanosilica").
• alumina is preferred from the perspective of being able to increase thermal conductivity.
• One type of inorganic filler (C) can be used alone, or two or more types can be used in combination.
• the shape of the inorganic filler (C) is not particularly limited, but examples include spherical (true spherical, nearly true spherical, etc.), polyhedral, rod-like (cylindrical, prismatic, etc.), plate-like, scaly, and irregular shapes. Of these, spherical shapes are preferred from the perspective of achieving a high loading amount.
• the average particle size of the inorganic filler (C) is not particularly limited, but is preferably 1 nm to 10 ⁇ m, more preferably 0.1 to 8 ⁇ m, and even more preferably 0.3 to 5 ⁇ m.
• the viscosity of the epoxy resin composition falls within an appropriate range, and a decrease in the gap filling speed tends to be less likely to occur.
• two or more fillers with different average particle sizes may be used in combination to adjust the viscosity of the epoxy resin composition.
• the method for measuring the average particle size of the inorganic filler (C) is not particularly limited, but it can be measured, for example, using a laser diffraction/scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).
• the content of inorganic filler (C) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more. It is also preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
• nanosilica When nanosilica is included, its content is not particularly limited, but is, for example, 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.1 to 10% by mass, and particularly preferably 0.3 to 5% by mass relative to the inorganic filler (C) (100% by mass).
• Core-shell rubber particles (D) have the effect of suppressing the occurrence and progression of fillet cracks when the epoxy resin composition is used as an underfill. Specifically, the incorporation of the core-shell rubber particles (D) reduces the modulus of elasticity of the cured product of the epoxy resin composition, thereby reducing the stress generated in the fillet portion and suppressing the occurrence of fillet cracks. Furthermore, if fillet cracks occur, the core-shell rubber particles (D) act as a stress relaxation agent and suppress the progression of the fillet cracks.
• Core-shell rubber particles (D) refer to rubber particles composed of a core and one or more shell layers covering the core.
• Core-shell rubber particles (D) have a core composed of a highly flexible material, and a shell layer composed of a material that has excellent affinity for the components contained in the epoxy resin composition, particularly the epoxy resin (A). This allows them to exhibit good dispersibility in the epoxy resin composition and achieve a low modulus of elasticity in the cured product.
• examples of materials that make up the core include silicone-based rubbers such as polydimethylsiloxane, butadiene-based rubbers, styrene-based rubbers, acrylic rubbers, polyolefin-based rubbers, and silicone/acrylic composite rubbers.
• Materials that make up the shell layer include monomers that have epoxy groups and monomers that do not have epoxy groups.
• the shell layer contains monomers that have epoxy groups and/or monomers that do not have epoxy groups as structural units.
• epoxy group-containing monomer examples include glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate, glycidyl methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether; and glycidyl group-containing vinyl monomers such as allyl glycidyl ether.
• glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate, glycidyl methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether
• glycidyl group-containing vinyl monomers such as allyl glycidyl ether.
• Examples of the monomer not having an epoxy group include unsaturated carboxylic acids, (meth)acrylates not having an epoxy group, aromatic vinyl compounds, and vinylcyan compounds.
• Examples of the unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, crotonic acid, and maleic anhydride.
• Examples of the (meth)acrylates not having an epoxy group include C1-5 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
• Examples of the aromatic vinyl compounds include vinylbenzenes such as styrene, ⁇ -methylstyrene, p-methylstyrene, and divinylbenzene.
• Examples of the vinylcyan compounds include acrylonitriles and methacrylonitriles.
• the epoxy resin composition of the present invention contains, as the core-shell rubber particles (D), core-shell rubber particles (D1) in which the shell layer contains (meth)acrylic acid and butyl (meth)acrylate as structural units.
• the epoxy resin composition may also contain core-shell rubber particles (D2) other than the core-shell rubber particles (D1).
• core-shell rubber particle (D) can be used alone, or two or more types can be used in combination.
• the viscosity of the epoxy resin composition can be adjusted to a low level, resulting in good handleability. Furthermore, the injectability of the epoxy resin composition is improved, allowing for efficient gap filling. Furthermore, because the core-shell rubber particles (D1) have the above properties, they can be added in larger amounts to the epoxy resin composition compared to conventional core-shell rubber particles. Therefore, it is possible to adjust the cured product of the epoxy resin composition to exhibit a lower elastic modulus.
• the average particle size of the core-shell rubber particles (D) is not particularly limited, but is preferably 0.03 to 1.0 ⁇ m, more preferably 0.04 to 0.8 ⁇ m, and even more preferably 0.05 to 0.7 ⁇ m.
• the average particle size of the core-shell rubber particles (D) can be measured, for example, by observing a cross-section of the cured product obtained by curing the epoxy resin composition using a scanning electron microscope (SEM).
• the content of the core-shell rubber particles (D) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less. Also, for example, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more.
• the content of the core-shell rubber particles (D1) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less. It is also preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more.
• the epoxy resin composition tends to have low viscosity and excellent injectability.
• the content of the core-shell rubber particles (D) relative to the total amount (100% by mass) of the epoxy resin (A) and curing agent (B) is not particularly limited, but is preferably 1 to 60% by mass, more preferably 1 to 45% by mass, and even more preferably 1 to 30% by mass.
• the core-shell rubber particles (D) can be produced by known or conventional means, for example, through the following core forming step and shell layer forming step.
• Core formation process This is a process for forming the material that forms the core. For example, this process includes forming polysiloxane by emulsion polymerization, and polymerizing a monomer containing alkyl (meth)acrylate in the presence of an emulsifier and an initiator to form an acrylic rubber.
• Shell layer formation process A process in which a monomer having an epoxy group and/or a monomer not having an epoxy group, and optionally an initiator, etc., are added to a system containing the core particles obtained in the core portion formation process, and the above monomers are copolymerized in the presence of the core particles to form a shell layer.
• the content of the curing accelerator (E) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably, for example, 0.01% by mass or more, and more preferably 0.02% by mass or more. Furthermore, although not particularly limited, it is preferably, for example, 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.
• the coupling agent (F) is not particularly limited, and examples thereof include various coupling agents such as vinyl-based, glycidoxy-based, methacryl-based, amino-based, mercapto-based, or imidazole-based silane coupling agents; alkoxide-based, chelate-based, or acylate-based titanium coupling agents; and long-chain spacer coupling agents such as glycidoxyoctyltrimethoxysilane or methacrylooctyltrimethoxysilane.
• the coupling agent (F) can be used alone or in combination of two or more.
• silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.
• the content of coupling agent (F) relative to the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. Furthermore, the content is not particularly limited, but is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less.
• the epoxy resin composition may contain components other than the epoxy resin (A), curing agent (B), inorganic filler (C), core-shell rubber particles (D), curing accelerator (E), and coupling agent (F) (hereinafter referred to as "other components (G)").
• other components (G) include curable compounds other than the epoxy resin (A), thermoplastic resins such as acrylic resins, polyethylene resins, polyester resins, polyurethane resins, and polyamide resins, ion trapping agents, surfactants, antioxidants, antifoaming agents, flame retardants, colorants, reactive diluents, and solvents.
• the other components (G) may be used alone or in combination of two or more.
• the content of the other component (G) relative to the epoxy resin composition (100% by mass) is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Also, although not particularly limited, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more.
• the epoxy resin (A) and inorganic filler (C) can be heated and mixed to uniformly disperse the inorganic filler (C) in the epoxy resin (A), followed by cooling as needed, and then mixing with components such as the curing agent (B) to prepare the epoxy resin composition.
• the above-mentioned epoxy resin composition can be preferably used as a material (semiconductor encapsulation epoxy resin composition) for encapsulating materials arranged on a substrate in a semiconductor device, such as semiconductor elements, wiring, and solder (solder bumps).
• a semiconductor encapsulation epoxy resin composition By using the above-mentioned epoxy resin composition as a semiconductor encapsulation epoxy resin composition, highly reliable semiconductor devices can be manufactured.
• the above-mentioned epoxy resin composition can also be preferably used as a material (flip-chip semiconductor encapsulation epoxy resin composition) for encapsulating semiconductor elements and the like arranged on a substrate in a flip-chip semiconductor device.
• the bump electrodes present in the gap can be encapsulated while also fixing the semiconductor element and the substrate together as an encapsulant, thereby improving reliability.
• the above-mentioned epoxy resin composition for semiconductor encapsulation can be used, for example, as an underfill such as capillary underfill, liquid mold underfill, secondary underfill, or pre-applied underfill, as a grab-top material, or as a liquid compression molding material.
• the above-mentioned epoxy resin composition is not limited to the above-mentioned use as an epoxy resin composition for semiconductor encapsulation, and can also be used, for example, as an adhesive for fixing, joining, or protecting components that make up electronic components.
• a cured product is formed by curing the epoxy resin composition.
• the curing method is not particularly limited, but for example, the curing can be carried out by subjecting the epoxy resin composition to a heat treatment.
• the temperature of the heat treatment is not particularly limited, but 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, but for example, 0.1 to 5 hours is preferred, and 0.5 to 3 hours is more preferred.
• the epoxy resin compositions of Examples 1 to 6 and Comparative Example 1 were prepared by mixing epoxy resin (A), curing agent (B), inorganic filler (C), and core-shell rubber particles (D), as well as at least one selected from the group consisting of curing accelerator (E), coupling agent (F), and other component (G), as needed, in the proportions shown in Table 1.
• the numerical values for each component in Table 1 indicate parts by mass.
• EH-105L modified aromatic amine-based curing agent, active hydrogen equivalent: 61 g/eq, manufactured by ADEKA Corporation
• Ethacure 100plus product name: diethyltoluenediamine, manufactured by Albemarle Corporation
• Table 1 The values in Table 1 are the mass of nanosilica, and the mass of bisphenol F type epoxy resin is added to YDF-8170.
• SE5050-SEJ product name: Silica with an average particle size of 1.5 ⁇ m, surface-treated with 3-glycidoxypropyltrimethoxysilane, manufactured by Admatechs Co., Ltd.
• Core-shell rubber particles Rubber particle 1: Core part / silicone rubber (polydimethylsiloxane), shell layer / core-shell rubber particle containing methacrylic acid, butyl acrylate, methyl methacrylate, and glycidyl methacrylate as structural units (corresponding to core-shell rubber particle (D1)), average particle size: 0.3 ⁇ m
• Rubber particle 2 Core part / silicone rubber (polydimethylsiloxane), shell layer / core-shell rubber particle containing methyl methacrylate, glycidyl methacrylate, styrene, and acrylonitrile as structural units (corresponding to core-shell rubber particle (D2)), average particle size: 0.3 ⁇ m Curing accelerator (E) CG-1400 / Product name "AMICURE CG-1400": Dicyandiamide, manufactured by Evonik Japan Co., Ltd.
• FIG. 1 represents a test specimen.
• 2 and 2' represent glass slides.
• 3 represents tape.
• 4 represents a gap.
• 5 represents an evaluation sample.
• (a) is a plan view of test specimen 1, with the longitudinal direction of test specimen 1 being vertical and the lateral direction being horizontal.
• (b) is a side view of test specimen 1 from the longitudinal direction.
• (c) is a side view of test specimen 1 from the lateral direction.
• Glass slide 2 is stacked on top of another glass slide 2' via tape 3.
• glass slide 2 and glass slide 2' are stacked so that there is a 1 cm misalignment in the longitudinal direction. This misalignment is the application area (sample application area) of evaluation sample 5.
• the evaluation results can be considered as follows: (1) From the viewpoint of the viscosity and injectability of the epoxy resin composition, it is preferable that the shell layer of the core-shell rubber particles contain butyl (meth)acrylate as a structural unit. This is thought to be due to the fact that, compared to when methyl (meth)acrylate or ethyl (meth)acrylate is contained as a structural unit, the number of carbon atoms in the side chain (acrylic group) is greater, thereby improving the wettability between the core-shell rubber particles and the epoxy resin (A).
• the epoxy resin composition of the present invention can be said to be effective in that it has the characteristics of both low viscosity and excellent injectability.
• [6] The epoxy resin composition according to any one of [1] to [5], wherein the content of the cyclohexane-type epoxy resin relative to the epoxy resin (A) (100% by mass) is 0 to 30% by mass.
• [7] The epoxy resin composition according to any one of [1] to [6], wherein the epoxy equivalent of the epoxy resin (A) is 30 to 1000 g/eq, 40 to 500 g/eq, or 50 to 300 g/eq.
• [8] The epoxy resin composition according to any one of [1] to [7], wherein the content of the epoxy resin (A) is 5% by mass or more, 8% by mass or more, 10% by mass or more, or 12% by mass or more, and/or 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less.
• the curing agent (B) is at least one selected from the group consisting of an amine-based curing agent, an acid anhydride-based curing agent, and a phenol-based curing agent, or is an amine-based curing agent.
• [15] The epoxy resin composition according to any one of [1] to [14], wherein the content of the inorganic filler (C) relative to the epoxy resin composition (100% by mass) is 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, and/or 90% by mass or less, 80% by mass or less, or 70% by mass or less.
• the epoxy resin composition according to [14], wherein the content of silica having an average particle size of 100 nm or less relative to the inorganic filler (C) (100% by mass) is 0.1 to 30% by mass, 0.1 to 20% by mass, 0.1 to 10% by mass, or 0.3 to 5% by mass.
• a semiconductor device comprising: the cured product according to [25] that encapsulates the semiconductor element.
• a method for manufacturing a semiconductor device comprising:
• the epoxy resin composition of the present invention has low viscosity and is therefore easy to handle. Furthermore, its excellent injectability allows the epoxy resin composition to be efficiently filled into gaps, even when manufacturing semiconductor devices using substrates such as large interposers. Furthermore, due to the above properties, it can contain a larger amount of core-shell rubber particles than conventional epoxy resin compositions. Therefore, it is possible to adjust the cured product of the epoxy resin composition so that it exhibits a low modulus of elasticity. Therefore, a semiconductor device comprising a cured product of the above epoxy resin composition can encapsulate semiconductor elements with high precision using the cured product, and demonstrates high reliability due to the reduced stress applied to the cured product of the epoxy resin composition.

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