Resin composition and semiconductor device

Abstract

To provide a resin composition capable of improving flowability of the resin composition and crack resistance of a cured product thereof.SOLUTION: A resin composition contains an epoxy compound (A), a liquid aromatic amine compound (B), and an inorganic filler (C). The epoxy compound (A) contains a liquid epoxy compound (A1) and a solid epoxy compound (A2). The solid epoxy compound (A2) contains a solid epoxy resin (a) which is at least one kind selected from a group consisting of an isocyanate modified epoxy resin, a naphthalene type epoxy resin, and a biphenyl type epoxy resin. The viscosity of the resin composition at 25°C is 400 Pa s or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure generally relates to a resin composition and a semiconductor device, and more particularly to a resin composition containing an epoxy compound and a semiconductor device including a sealing portion made of the resin composition.

Background Art

[0002] Patent Document 1 discloses a liquid epoxy resin composition containing an aminophenol type epoxy resin, an amine-based curing agent, a silica filler, and a silane coupling agent, including 10.0 to 70 parts by mass of the aminophenol type epoxy resin with respect to 100 parts by mass of the liquid epoxy resin, where the amine-based curing agent is in a ratio of 0.7 to 1.2 equivalents with respect to 1 equivalent of the liquid epoxy resin, and the glass transition temperature after curing is 110 to 200°C. Patent Document 1 describes that this liquid epoxy resin composition is excellent in injectability into a flip-chip type semiconductor device having a fine pitch wiring pattern and suppresses fillet cracks after curing.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] When a semiconductor device is enlarged, it is likely to be damaged when an impact, stress, or thermal load is applied to the sealing portion in the semiconductor device. In this case, further crack resistance is required for the sealing portion.

[0005] An object of the present disclosure is to provide a resin composition capable of enhancing the crack resistance of a cured product and a semiconductor device including a sealing portion made of the cured product of this resin composition.

Means for Solving the Problems

[0006] A resin composition according to one aspect of the present disclosure contains an epoxy compound (A), a liquid aromatic amine compound (B), and an inorganic filler (C). The epoxy compound (A) contains a liquid epoxy compound (A1) and a solid epoxy compound (A2). The solid epoxy compound (A2) contains a solid epoxy resin (a) which is at least one selected from the group consisting of an isocyanate-modified epoxy resin, a naphthalene-type epoxy resin, and a biphenyl-type epoxy resin. The viscosity of the resin composition at 25°C is 400 Pa·s or less.

[0007] A semiconductor device according to one aspect of the present disclosure includes a substrate, a semiconductor element mounted on the substrate, and a sealing portion filled in a gap between the substrate and the semiconductor. The sealing portion contains a cured product of the resin composition.

Effect of the Invention

[0008] According to one aspect of the present disclosure, a resin composition capable of enhancing the crack resistance of a cured product, and a semiconductor device including a sealing portion containing a cured product of this resin composition can be provided.

Brief Description of the Drawings

[0009]

Figure 1

Modes for Carrying Out the Invention

[0010] 1. Overview Embodiments of the present disclosure will be described. Note that the following embodiments are only a part of various embodiments of the present disclosure. Further, the following embodiments can be variously modified according to design and the like as long as the object of the present disclosure can be achieved. The drawings referred to below are schematic drawings, and the dimensional ratios of the components in the drawings do not necessarily reflect the actual dimensional ratios. Although the mechanism of action in the embodiments may be described below, the description of this mechanism of action includes descriptions based on speculation, and the present disclosure is not restricted by the description of the mechanism of action.

[0011] The resin composition of the embodiment (hereinafter also referred to as composition (X)) contains an epoxy compound (A), a liquid aromatic amine compound (B), and an inorganic filler (C). The epoxy compound (A) contains a liquid epoxy compound (A1) and a solid epoxy compound (A2). The solid epoxy compound (A2) contains a solid epoxy resin (a) which is at least one selected from the group consisting of an isocyanate-modified epoxy resin, a naphthalene-type epoxy resin, and a biphenyl-type epoxy resin. The viscosity of the composition (X) at 25°C is 400 Pa·s or less.

[0012] According to the embodiment, the crack resistance of the cured product of the composition (X) can be improved.

[0013] The composition (X) can be used for manufacturing a semiconductor device. More specifically, the composition (X) can be used for manufacturing a sealing portion provided in the semiconductor device. In particular, the composition (X) can be suitably used for manufacturing a sealing portion for filling a semiconductor element on a substrate when the semiconductor element is flip-chip mounted on the substrate. That is, the composition (X) can be suitably used as an underfill material. In this case, the composition (X) easily flows between the semiconductor element and the substrate during the production of the sealing portion, so that the manufacturing efficiency of the semiconductor device is increased, and unfilling of the sealing portion can be suppressed. Further, when a load such as impact, stress, or heat is applied to the sealing portion, cracks are less likely to occur in the sealing portion. Therefore, the reliability of the semiconductor device can be increased.

[0014] Note that the use of the composition (X) is not limited to only encapsulating semiconductor elements. The composition (X) can be used for various applications other than encapsulating semiconductor elements.

[0015] Hereinafter, the embodiments will be described in more detail.

[0016] 2. Composition As described above, the composition (X) contains an epoxy compound (A), a liquid aromatic amine compound (B), and an inorganic filler (C).

[0017] The epoxy compound (A) preferably contains a compound having two or more epoxy groups in one molecule. In this case, the reactivity between the epoxy compound (A) and the aromatic amine (B) can be further enhanced. As a result, the heat resistance and crack resistance of the cured product of the composition (X) can be further improved.

[0018] As described above, the epoxy compound (A) contains a liquid epoxy compound (A1) and a solid epoxy compound (A2). "Liquid" means having fluidity at 25°C. "Solid" means not having fluidity at 25°C. The liquid epoxy compound (A1) can impart fluidity to the composition (X). The epoxy compound (A) is preferably liquid as a whole by mixing the liquid epoxy compound (A1) and the solid epoxy compound (A2). In this case, the epoxy compound (A) can impart good fluidity to the composition (X).

[0019] The viscosity of the epoxy compound (A) at 25°C is preferably 100 Pa·s or less. More preferably, the viscosity is 50 Pa·s or less, and even more preferably 20 Pa·s or less. Also, the viscosity of the epoxy compound (A) at 25°C is, for example, 0.01 Pa·s or more. More preferably, this viscosity is 0.02 Pa·s or more.

[0020] The viscosity of the liquid epoxy compound (A1) at 25°C is preferably 100 Pa·s or less. More preferably, the viscosity is 50 Pa·s or less, and even more preferably 20 Pa·s or less. Also, the viscosity of the liquid epoxy compound (A1) at 25°C is, for example, 0.01 Pa·s or more. More preferably, this viscosity is 0.02 Pa·s or more.

[0021] The liquid epoxy compound (A1) contains at least one selected from the group consisting of, for example, diglycidyl ether type epoxy resins such as p-aminophenol type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and hydrogenated bisphenol A type epoxy resin; epoxy resins obtained by epoxidizing novolak resins obtained by the reaction of phenols and aldehydes typified by orthocresol novolak type epoxy resin; glycidyl ester type epoxy resins obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidyl amine type epoxy resins obtained by the reaction of amine compounds such as aminodiphenylmethane and isocyanuric acid with epichlorohydrin; and silicone-modified epoxy resins (b).

[0022] The liquid epoxy compound (A1) preferably contains a silicone-modified epoxy resin (b). In this case, the fluidity of the composition (X) can be further increased. Furthermore, the silicone-modified epoxy resin (a1) is less likely to lower the glass transition temperature of the cured product of the composition (X) and is less likely to cause weight loss of the cured product under heating. This is considered to be because the silicone skeleton of the silicone-modified epoxy resin (a1) has high heat resistance and the bond between silicon and oxygen in the silicone skeleton makes the molecular chain of the silicone-modified epoxy resin (a1) flexible, thereby reducing the viscosity of the composition (X).

[0023] When the liquid epoxy compound (A1) contains the silicone-modified epoxy resin (b), the amount of the silicone-modified epoxy resin (b) is preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A). When this amount is 5 parts by mass or more, the fluidity of the composition (X) can be further enhanced. If this amount is 7 parts by mass or more, it is more preferable, and if it is 10 parts by mass or more, it is even more preferable. When this amount is 30 parts by mass or less, there is an advantage that the weight loss when the composition (X) is heated and cured can be more suppressed. If this amount is 25 parts by mass or less, it is more preferable, and if it is 20 parts by mass or less, it is even more preferable.

[0024] It is also preferable that the liquid epoxy compound (A1) contains at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, p-aminophenol type epoxy resin, and naphthalene type epoxy resin. In this case, the curability of the composition (X) can be particularly enhanced.

[0025] The liquid epoxy compound (A1) may contain a commercially available product. For example, the liquid epoxy compound (A1) may contain at least one selected from the group consisting of bisphenol F type epoxy resin (product name: YDF-8170C, epoxy equivalent: 155 - 165 g / eq) manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol A type epoxy resin (product name: YD-128, epoxy equivalent: 184 - 194 g / eq) manufactured by Nippon Steel Chemical & Material Co., Ltd., and polyfunctional epoxy resin (product name: jER-630, epoxy equivalent: 90 - 105 g / eq) manufactured by Mitsubishi Chemical Corporation, etc.

[0026] The liquid epoxy compound (A1) preferably contains a liquid epoxy compound (A11) having an epoxy equivalent of 100 g / eq. or more. In this case, the crack resistance of the cured product can be further improved. This is presumably because the crosslink density of the cured product becomes moderately low. Note that the liquid epoxy compound (A11) may or may not contain the above silicone-modified epoxy resin (b). If the epoxy equivalent of the liquid epoxy compound (A11) is 160 g / eq. or more, it is more preferable. This epoxy equivalent is, for example, 1000 g / eq. or less, and more preferably 500 g / eq. or less.

[0027] It is also preferable that the overall epoxy equivalent (average epoxy equivalent) of the liquid epoxy compound (A1) is 100 g / eq. or more. In this case, the crack resistance of the cured product can be further improved. This is presumably because the crosslink density of the cured product becomes moderately low. If the epoxy equivalent of the liquid epoxy compound (A1) is 160 g / eq. or more, it is more preferable. This epoxy equivalent is, for example, 1000 g / eq. or less, and more preferably 500 g / eq. or less.

[0028] As described above, the solid epoxy compound (A2) contains at least one solid epoxy resin (a) selected from the group consisting of an isocyanate-modified epoxy resin, a naphthalene-type epoxy resin, and a biphenyl-type epoxy resin.

[0029] The isocyanate-modified epoxy resin is an epoxy resin having a structure formed from an isocyanate group in the molecule. The structure formed from the isocyanate group is, for example, an oxazolidone ring, an isocyanurate ring, a urethane bond, or a carbonate bond. The naphthalene-type epoxy resin is an epoxy resin having a naphthalene ring in the molecule, and the biphenyl-type epoxy resin is an epoxy resin having a biphenyl skeleton in the molecule.

[0030] The solid epoxy resin (a) can improve the crack resistance of the cured product and increase the glass transition temperature of the cured product. For example, although there are reports that the crack resistance of the cured product can be improved by an aminophenol type epoxy resin, with the increase in the size of semiconductor devices, further crack resistance is required for the sealing part. In the embodiment, the solid epoxy compound (A2) contains the solid epoxy resin (a), thereby improving the crack resistance of the cured product. That is, by selecting the components contained in the epoxy compound (A), the crack resistance of the cured product can be improved. The reason has not been fully clarified, but it is considered that the solid epoxy resin (a) moderately lowers the crosslinking density of the cured product, and this contributes to the improvement of the crack resistance due to the improvement of the flexibility of the cured product. Furthermore, the solid epoxy resin (a) can increase the glass transition temperature of the cured product. This is presumably because the solid epoxy resin (a) has a rigid molecular structure.

[0031] The epoxy equivalent of each of the isocyanate-modified epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin is preferably 180 g / eq. or more. In this case, the crack resistance of the cured product can be further improved. This epoxy equivalent is more preferably 200 g / eq or more, and even more preferably 220 g / eq or more. Also, this epoxy equivalent is, for example, 1000 g / eq or less, and more preferably 500 g / eq or less.

[0032] It is also preferable that the total epoxy equivalent (average epoxy equivalent) of the solid epoxy resin (a) is 180 g / eq. or more. In this case, the crack resistance of the cured product can be further improved. This epoxy equivalent is more preferably 200 g / eq or more, and even more preferably 220 g / eq or more. Also, this epoxy equivalent is, for example, 1000 g / eq or less, and more preferably 500 g / eq or less.

[0033] The proportion of the epoxy compound (a) is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A). If this proportion is 3 parts by mass or more, the crack resistance of the cured product can be further improved, and the glass transition temperature of the cured product can be increased. If this proportion is 5 parts by mass or more, it is more preferable, and if it is 10 parts by mass or more, it is even more preferable. If this proportion is 30 parts by mass or less, the fluidity of the composition (X) can be increased. If this proportion is 25 parts by mass or less, it is more preferable, and if it is 20 parts by mass or less, it is even more preferable.

[0034] The solid epoxy compound (A2) may contain only the epoxy compound (a), or may contain, in addition to the epoxy compound (a), a compound other than the epoxy compound (a) (hereinafter also referred to as the epoxy compound (c)). When the solid epoxy compound (A2) contains the epoxy compound (c), the proportion of the epoxy compound (c) is, for example, 20 parts by mass or less with respect to 100 parts by mass of the solid epoxy compound (A2), preferably 10 parts by mass or less.

[0035] The amount of the solid epoxy compound (A2) is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A). If this amount is 3 parts by mass or more, the crack resistance of the cured product can be further improved, and the glass transition temperature of the cured product can be increased. If this amount is 5 parts by mass or more, it is more preferable, and if it is 10 parts by mass or more, it is even more preferable. If this amount is 30 parts by mass or less, the fluidity of the composition (X) can be increased. If this amount is 25 parts by mass or less, it is more preferable, and if it is 20 parts by mass or less, it is even more preferable.

[0036] As described above, the aromatic amine (B) is liquid. All the components contained in the aromatic amine (B) may be liquid, or the aromatic amine (B) may contain a liquid component and a solid component, and the aromatic amine (B) may be liquid as a whole when the components are mixed. The liquid aromatic amine (B) can impart fluidity to the composition (X).

[0037] The aromatic amine (B) preferably contains an aromatic amine (C1) having two or more amino groups in one molecule. In this case, the reactivity between the epoxy compound (A) and the aromatic amine (B) can be further enhanced. As a result, the curability of the composition (X) can be further enhanced, and the heat resistance of the cured product of the composition (X) can be further enhanced.

[0038] The aromatic amine (B) contains, for example, at least one selected from the group consisting of aliphatic aromatic amines such as m-xylylenediamine, aromatic amines having one aromatic ring such as metaphenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole, and dimethylthiotoluenediamine, aromatic amines having two aromatic rings such as 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, and polytetramethylene oxide diparaaminobenzoate, condensates of aromatic diamines and epichlorohydrin, reaction products of aromatic diamines and styrene, and the like.

[0039] The aromatic amine (B) particularly preferably contains at least one selected from the group consisting of diethyltoluenediamine and dimethylthiotoluenediamine. In this case, the storage stability of the composition (X) can be further enhanced.

[0040] The aromatic amine (B) may contain commercially available products. For example, the aromatic amine (B) may contain at least one selected from the group consisting of amine curing agents manufactured by Nippon Kayaku Co., Ltd. (product name: KAYAHARD A-A, amine active hydrogen equivalent: 63.5 g / eq), modified aromatic amine curing agents manufactured by ADEKA Corporation (product name: EH-105L, amine active hydrogen equivalent: 61 g / eq), and the like.

[0041] The amine active hydrogen equivalent of the aromatic amine (B) is, for example, 20 g / eq. or more and 500 g / eq. or less. In this case, the reactivity between the epoxy compound (A) and the aromatic amine (B) can be enhanced. The amine active hydrogen equivalent means the mass (g) of the aromatic amine (B) containing 1 mol of amine active hydrogen. The amine active hydrogen equivalent of the aromatic amine (B) is preferably 30 g / eq. or more, for example. The amine active hydrogen equivalent of the aromatic amine (B) is preferably 100 g / eq. or less, for example.

[0042] The equivalent ratio of the amine active hydrogen of the aromatic amine (B) to the epoxy group of the epoxy compound (A) is preferably 0.6 or more and 1.4 or less. In this case, the epoxy compound (A) and the aromatic amine (B) can react efficiently. Therefore, the glass transition temperature of the cured product can be moderately increased, and the crack resistance of the cured product can also be increased. It is more preferably 0.7 or more, and even more preferably 0.8 or more, for this equivalent. It is also more preferable that this equivalent ratio is 1.3 or less.

[0043] The inorganic filler (C) can contribute to reducing the linear expansion coefficient of the cured product, and thereby contribute to suppressing warping and breakage of the semiconductor device. The inorganic filler (C) can also contribute to improving the thermal conductivity of the cured product, and thereby the heat dissipation of the semiconductor device can be increased.

[0044] The inorganic filler (C) contains, for example, one or more materials selected from the group consisting of silica such as fused silica, synthetic silica, crystalline silica, and hollow silica; metal oxides such as alumina and titanium oxide; silicates such as talc, fired clay, unfired clay, mica, and glass; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. The fused silica may be either fused spherical silica or fused crushed silica.

[0045] The inorganic filler (C) preferably contains silica in particular. In this case, silica can particularly contribute to increasing the high elasticity, decreasing the linear expansion coefficient, and decreasing the dielectric tangent of the cured product.

[0046] The particle shape of the inorganic filler (C) may be crushed, needle-like, scaly, spherical, etc., and is not particularly limited. For improving the dispersibility of the inorganic filler (C) in the composition (X) and for controlling the viscosity of the composition (X), the particle shape of the inorganic filler (C) is preferably spherical.

[0047] It is preferable that the particles of the inorganic filler (C) are surface-treated with a surface treatment agent. In this case, the dispersibility of the inorganic filler (C) in the composition (X) can be enhanced. Thereby, the decrease in the fluidity of the composition (X) due to the inorganic filler (C) can be suppressed. The surface treatment agent contains at least one selected from the group consisting of, for example, silane-based compounds, titanium-based compounds, aluminum chelates, and aluminum / zirconium-based compounds.

[0048] The silane-based compound contains at least one selected from the group consisting of, for example, silane compounds having an amino group, epoxy silane, mercapto silane, alkyl silane, ureido silane, and vinyl silane.

[0049] Specifically, the silane compound contains at least one selected from the group consisting of, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane, etc.

[0050] The average particle diameter of the inorganic filler (C) is, for example, 0.1 μm or more and 70 μm or less. In this case, the composition (X) can have good fluidity. It is more preferable that the average particle diameter of the inorganic filler (C) is 0.3 μm or more. It is also more preferable that the average particle diameter of the inorganic filler (C) is 20 μm or less. The average particle diameter is the volume-based median diameter calculated from the measurement values of the particle size distribution by the laser diffraction / scattering method, and can be measured using a commercially available laser diffraction / scattering type particle size distribution measuring device.

[0051] The inorganic filler (C) preferably contains a first inorganic filler (C1) having an average particle diameter of more than 0.1 μm and 15 μm or less, and a second inorganic filler (C2) having an average particle diameter of 0.1 μm or less. In this case, the increase in the viscosity of the composition (X) due to the inorganic filler (C) can be further suppressed. Thereby, the composition (X) can have better fluidity.

[0052] The average particle diameter of the first inorganic filler (C1) is more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. The average particle diameter of the first inorganic filler (C1) is more preferably 5 μm or less, and even more preferably 2 μm or less. The average particle diameter of the second inorganic filler (C2) is more preferably 5 nm or more, and even more preferably 10 nm or more. The average particle diameter of the second inorganic filler (C2) is more preferably 80 nm or less, and even more preferably 60 nm or less.

[0053] When the inorganic filler (C) contains the first inorganic filler (C1) and the second inorganic filler (C2), the amount of the second inorganic filler (C2) is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first inorganic filler (C1). In this case, the increase in the viscosity of the composition (X) can be further suppressed. It is more preferable that the amount of the second inorganic filler (C2) is 2 parts by mass or more. It is also more preferable that the amount of the second inorganic filler (C2) is 8 parts by mass or less.

[0054] The first inorganic filler (C1) may contain silica and may contain only silica. The second inorganic filler (C2) may also contain silica and may contain only silica.

[0055] It is particularly preferable that the first inorganic filler (C1) contains silica surface-treated with at least one selected from the group consisting of phenylaminosilane compounds, phenylsilane compounds, epoxysilane compounds, and methacryl silane compounds. In this case, the fluidity of the composition (X) can be further improved, and the storage stability of the composition (X) can be further enhanced. In the composition (X) containing the epoxy compound (A), the aromatic amine compound (B), and the inorganic filler (C), when the inorganic filler (C) is treated with a surface treatment agent, the storage stability may decrease. However, if the first inorganic filler (C1) contains silica surface-treated with any of the above silane compounds, a decrease in the storage stability of the composition (X) can be suppressed. Examples of the phenylaminosilane compound include N-phenyl-3-aminopropyltrimethoxysilane. Examples of the phenylsilane compound include phenyltrimethoxysilane. The epoxysilane compound contains at least one selected from the group consisting of, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The methacryl silane compound contains at least one selected from the group consisting of, for example, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.

[0056] The total ratio of the first inorganic filler (C1) and the second inorganic filler (C2) to the inorganic filler (C) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. The inorganic filler (C) may contain only the first inorganic filler (C1) and the second inorganic filler (C2).

[0057] The proportion of the inorganic filler (C) is preferably 40% by mass or more and 80% by mass or less based on the total amount of the composition (X). When the proportion of the inorganic filler (C) is 40% by mass or more, the linear expansion coefficient of the composition (X) can be further reduced. Thereby, the crack resistance of the cured product of the composition (X) can be enhanced. When the proportion of the inorganic filler (C) is 80% by mass or less, the composition (X) can have good fluidity. The proportion of the inorganic filler (C) is more preferably 42% by mass or more, and even more preferably 45% by mass or more. The proportion of the inorganic filler (C) is more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0058] The composition (X) may contain rubber particles (D). When the composition (X) contains rubber particles (D), the cured product has a lower elastic modulus, and the crack resistance of the cured product can be further enhanced.

[0059] The rubber particles (D) preferably contain at least one of silicone rubber particles and butadiene rubber particles. It is easy to make the cured product have a lower elastic modulus.

[0060] The silicone rubber particles can contain, for example, silicone-based core-shell particles, specifically, commercially available products such as Kaneka Ace (registered trademark) MX-962 manufactured by Kaneka Corporation, etc., but are not limited thereto. The butadiene rubber particles can contain, for example, butadiene-based core-shell particles, specifically, commercially available products such as Kaneka Ace (registered trademark) MX-136 manufactured by Kaneka Corporation, etc., but are not limited thereto.

[0061] The proportion of the rubber particles (D) with respect to the composition (X) is preferably 0.1% by mass or more and 3.0% by mass or less. If the proportion is 0.1% by mass or more, the crack resistance of the cured product can be particularly enhanced. If this proportion is 0.3% by mass or more, it is more preferable, and if it is 0.5% by mass or more, it is even more preferable. When the proportion of the rubber particles (E) is 3.0% by mass or less, there is an advantage that the viscosity increase of the composition (X) is less likely to occur. If this proportion is 2.5% by mass or less, it is more preferable, and if it is 2.0% by mass or less, it is even more preferable.

[0062] The composition (X) may contain an organophosphorus compound (E). When the composition (X) contains the organophosphorus compound (E), the storage stability of the composition (X) can be further enhanced.

[0063] The organophosphorus compound (E) contains at least one selected from the group consisting of, for example, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, and tris(tetraalkylphenyl)phosphine.

[0064] The ratio of the organophosphorus compound (E) to the composition (X) is preferably 0.03% by mass or more and 0.70% by mass or less. If the ratio is 0.03% by mass or more, the storage stability of the composition (X) can be further improved. More preferably, this ratio is 0.05% by mass or more, and still more preferably 0.10% by mass or more. If the ratio of the organophosphorus compound (E) is 0.70% by mass or less, there is an advantage that a decrease in the glass transition temperature of the cured product can be suppressed, that is, a decrease in the heat resistance of the cured product can be suppressed. More preferably, this ratio is 0.60% by mass or less, and still more preferably 0.50% by mass or less.

[0065] The composition (X) may contain an aluminum complex (F). When the composition (X) contains the aluminum complex (F), the fluidity of the composition (X) can be further enhanced.

[0066] The aluminum complex (F) contains at least one selected from the group consisting of, for example, aluminum trisacetylacetonate and aluminum bisethylacetoacetate·monoacetylacetonate.

[0067] The proportion of the aluminum complex (F) relative to the total of the epoxy compound (A) and the aromatic amine compound (B) is preferably 0.03% by mass or more and 0.30% by mass or less. If the proportion is 0.03% by mass or more, the fluidity of the composition (X) can be further improved. If this proportion is 0.05% by mass or more, it is more preferable, and if it is 0.10% by mass or more, it is even more preferable. If the proportion of the aluminum complex (F) is 0.30% by mass or less, there is an advantage that the deterioration of the storage stability of the composition (X) can be suppressed. If this proportion is 0.25% by mass or less, it is more preferable, and if it is 0.20% by mass or less, it is even more preferable.

[0068] The composition (X) may contain additives other than the above components, if necessary. The additives are preferably contained within a range that does not excessively impair the above-described properties of the composition (X).

[0069] The additives may contain at least one selected from the group consisting of, for example, resin modifiers, antioxidants, curing aids, coupling agents, colorants, thixotropic agents, ion trap agents, defoaming agents, leveling agents, and antioxidants.

[0070] Preferably, the composition (X) does not contain a solvent or contains only a trace amount of solvent unavoidably mixed in.

[0071] The viscosity of the composition (X) at 25°C is 400 Pa·s or less. Therefore, the composition (X) can have good fluidity. If this viscosity is 200 Pa·s or less, it is more preferable, and if it is 120 Pa·s or less, it is even more preferable. Also, the viscosity of the composition (X) at 25°C may be, for example, 5 Pa·s or more and 10 Pa·s or more. The viscosity of this composition (X) can be realized by appropriately setting the composition of the composition (X) within the range described above. The method for measuring the viscosity is described in the Examples section.

[0072] The glass transition temperature of the cured product of the composition (X) is preferably 80°C or higher. In this case, the cured product can have good heat resistance. The glass transition temperature is more preferably 100°C or higher, and even more preferably 130°C or higher. Further, the glass transition temperature is, for example, 180°C or lower. The method for measuring the glass transition temperature is described in the Examples section.

[0073] 3. Semiconductor device Fig. 1 shows an example of the semiconductor device 1. The composition (X) in the embodiment is for semiconductor encapsulation. That is, the encapsulation part 5 in the semiconductor device 1 can be fabricated from the composition (X). The encapsulation part 5 is a component that protects the semiconductor element 3 by covering part or all of the semiconductor element 3 in the semiconductor device 1.

[0074] The composition (X) can be used as an underfill material. The underfill material is a material for forming the encapsulation part 5 filled in the gap between the substrate 2 and the semiconductor element 3 surface-mounted on the substrate 2. That is, in this case, the semiconductor device 1 includes the substrate 2, the semiconductor element 3 mounted on the substrate 2, and the encapsulation part 5 filled in the gap between the substrate 2 and the semiconductor element 3, and the encapsulation part 5 contains the cured product of the composition (X).

[0075] The substrate 2 includes, for example, an insulating substrate such as a glass epoxy substrate, a polyimide substrate, a polyester substrate, or a ceramic substrate, and a conductor wiring 21 overlapping on the insulating substrate. The conductor wiring 21 includes, for example, electrode pads. The substrate 2 is, for example, a mother board, a package substrate, or an interposer substrate.

[0076] The semiconductor element 3 may be any surface-mount type element. The semiconductor element 3 is provided with bump electrodes 31 on the surface facing the substrate 2. The semiconductor element 3 may be a bare chip, a packaged component, or a wafer-level package. The semiconductor element 3 is a flip-chip type chip such as, for example, BGA (Ball Grid Array), LGA (Land Grid Array), or CSP (Chip Size Package). The semiconductor element 3 may be a PoP (Package on Package) type chip.

[0077] The semiconductor element 3 is surface-mounted on the substrate 2. Specifically, the surface of the semiconductor element 3 having the bump electrodes 31 faces the substrate 2, and the bump electrodes 31 in the semiconductor element 3 and the electrode pads of the conductor wiring 21 in the substrate 2 are joined by solder bumps 4, and the bump electrodes 31 and the electrode pads are electrically connected by the solder bumps 4. Note that if the semiconductor element 3 is mounted on the substrate 2 such that a gap is formed between the semiconductor element 3 and the substrate 2, the connection mode between the semiconductor element 3 and the substrate 2 is not limited to the above.

[0078] The sealing portion 5 is filled in the gap between the semiconductor element 3 and the substrate 2, and thus the bump electrodes 31, the solder bumps 4, and the electrode pads of the conductor wiring 21 are buried in the sealing portion 5.

[0079] In the embodiment, since the composition (X) can have a high glass transition temperature, the semiconductor device 1 can have high heat resistance.

[0080] An example of the manufacturing method of the semiconductor device 1 will be described. First, the above-described substrate 2, semiconductor element 3, and composition (X) are prepared.

[0081] The semiconductor element 3 is surface-mounted on the substrate 2. Specifically, the surface of the semiconductor element 3 having the bump electrodes 31 is opposed to the substrate 2, and solder bumps 4 are interposed between the bump electrodes 31 in the semiconductor element 3 and the electrode pads of the conductor wiring 21 in the substrate 2. The solder contained in the solder bumps 4 is lead-free solder having a melting point of 210°C or higher, such as Sn-3.5Ag (melting point 221°C), Sn-2.5Ag-0.5Cu-1Bi (melting point 214°C), Sn-0.7Cu (melting point 227°C), or Sn-3Ag-0.5Cu (melting point 217°C). In this state, the solder bumps 4 are heated and melted and then solidified by an appropriate heating method such as reflow heating. The heating temperature is appropriately set according to the solder bumps 4 so that the solder bumps 4 are melted. For example, the maximum heating temperature is 180°C or higher and 300°C or lower. Thereby, the conductor wiring 21 and the electrode pads are joined by the solder bumps 4, and the conductor wiring 21 and the electrode pads are electrically connected by the solder bumps 4.

[0082] Next, the composition (X) is injected into the gap between the semiconductor element 3 and the substrate 2 by a dispenser or the like. The composition (X) flows through the gap between the semiconductor element 3 and the substrate 2 by capillary action. When flowing the composition (X), if necessary, the viscosity of the composition (X) may be reduced by heating the composition (X). The heating temperature of the composition (X) in this case is, for example, 80°C or higher and 130°C or lower. Thereby, the gap between the semiconductor element 3 and the substrate 2 is filled with the composition (X). In this state, the composition (X) is cured by heating. The heating conditions in this case are appropriately set according to the composition of the composition (X). For example, the heating temperature is 80°C or higher and 180°C or lower, and the heating time is 60 minutes or longer and 300 minutes or shorter. Thereby, a sealing portion 5 including a cured product of the composition (X) is formed in the gap between the semiconductor element 3 and the substrate 2.

[0083] In the embodiment, since the composition (X) can have high fluidity, the occurrence of unfilled portions of the composition (X) and the sealing portion 5 between the semiconductor element 3 and the substrate 2 can be suppressed.

[0084] Note that the manufacturing method of the semiconductor device 1 is not limited to the above only.

[0085] 4. Aspects The composition (X) according to the first aspect of the present disclosure contains an epoxy compound (A), a liquid aromatic amine compound (B), and an inorganic filler (C). The solid epoxy compound (A2) contains a solid epoxy resin (a) which is at least one selected from the group consisting of an isocyanate-modified epoxy resin, a naphthalene-type epoxy resin, and a biphenyl-type epoxy resin. The viscosity of the composition (X) at 25°C is 400 Pa·s or less.

[0086] According to this aspect, the crack resistance of the cured product of the composition (X) can be enhanced.

[0087] In the second aspect, in the first aspect, the liquid epoxy compound (A1) contains a liquid epoxy compound (A11) having an epoxy equivalent of 100 g / eq. or more.

[0088] According to this aspect, the crack resistance of the cured product of the composition (X) can be further enhanced.

[0089] In the third aspect, in the first or second aspect, the amount of the solid epoxy compound (A2) is 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A).

[0090] According to this aspect, the crack resistance of the cured product of the composition (X) can be further enhanced, the glass transition temperature of the cured product can be further increased, and the fluidity of the composition (X) can be enhanced.

[0091] In the fourth aspect, in any one of the first to third aspects, the inorganic filler (C) contains a first inorganic filler (C1) having an average particle diameter of more than 0.1 μm and 15 μm or less, and a second inorganic filler (C2) having an average particle diameter of 0.1 μm or less. The amount of the second inorganic filler (C2) is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first inorganic filler (C1).

[0092] According to this aspect, the fluidity of the composition (X) can be further enhanced.

[0093] In a fifth aspect, in any one of the first to fourth aspects, the first inorganic filler (C1) contains silica surface-treated with at least one selected from the group consisting of phenylaminosilane compounds, phenylsilane compounds, epoxysilane compounds, and methacryl silane compounds.

[0094] According to this aspect, the fluidity and storage stability of the composition (X) can be enhanced.

[0095] In a sixth aspect, in any one of the first to fifth aspects, the liquid epoxy compound (A1) contains a silicone-modified epoxy resin (b).

[0096] According to this aspect, the fluidity of the composition (X) can be enhanced.

[0097] In a seventh aspect, in the sixth aspect, the amount of the silicone-modified epoxy resin (b) is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A).

[0098] According to this aspect, the fluidity of the composition (X) can be enhanced.

[0099] In an eighth aspect, in any one of the first to seventh aspects, the composition (X) further contains rubber particles (D).

[0100] According to this aspect, the crack resistance of the cured product can be further enhanced.

[0101] In a ninth aspect, in the eighth aspect, the rubber particles (D) contain at least one of butadiene rubber particles and silicone rubber particles.

[0102] According to this aspect, the crack resistance of the cured product can be further enhanced.

[0103] In the tenth aspect, in any one of the first to ninth aspects, the composition (X) further contains an organic phosphorus compound (E).

[0104] According to this aspect, the fluidity of the composition can be enhanced.

[0105] In the eleventh aspect, in any one of the first to tenth aspects, the composition (X) is for semiconductor encapsulation.

[0106] In the twelfth aspect, in any one of the first to eleventh aspects, the composition (X) is an underfill material.

[0107] The semiconductor device (1) according to the thirteenth aspect includes a substrate (2), a semiconductor element (3) mounted on the substrate (2), and a sealing portion (5) filled in the gap between the substrate (2) and the semiconductor element (3). The sealing portion (5) includes a cured product of the resin composition according to any one of the first to twelfth aspects.

Examples

[0108] Hereinafter, specific examples of the embodiments will be described. Note that the present disclosure is not limited by these examples.

[0109] 1. Preparation of Composition The components shown in Tables 1 to 3 were mixed to prepare a composition. The details of the components in Tables 1 to 3 are as follows. - Liquid epoxy compound #1: Manufactured by Nippon Steel Chemical & Material Co., Ltd. Product name: YDF8170. Liquid bisphenol F type epoxy resin. Epoxy equivalent: 160 g / eq. - Liquid epoxy compound #2: Manufactured by Momentive Performance Materials Japan LLC. Product name: TSL9906. Liquid silicone-modified epoxy resin (siloxane oligomer having glycidoxypropyl groups at both ends). Epoxy equivalent: 181 g / eq. - Liquid epoxy compound #3: Manufactured by ADEKA Corporation. Product name: EP-3950S. Liquid aminophenol type epoxy resin. Epoxy equivalent: 94 g / eq. - Solid epoxy compound #1: Manufactured by Asahi Kasei Corporation. Product name: AER-4004. Isocyanate-modified epoxy resin. Epoxy equivalent: 390 g / eq. - Solid epoxy compound #2: Manufactured by Asahi Kasei Corporation. Product name: AER-4001. Isocyanate-modified epoxy resin. Epoxy equivalent: 290 g / eq. - Solid epoxy compound #3: Manufactured by DIC Corporation. Product name: EXA-7311-G4S. Naphthalene-type epoxy resin. Epoxy equivalent: 186 g / eq. - Solid epoxy compound #4: Manufactured by Nippon Kayaku Co., Ltd. Product name: NC3000-L. Biphenyl-type epoxy resin. Epoxy equivalent: 240 g / eq. - Solid epoxy compound #5: Tetrakis(glycidyloxyphenyl)ethane. Tetrakisphenol ethane-type epoxy resin. Epoxy equivalent: 168 g / eq. - Hardener: Manufactured by Nippon Kayaku Co., Ltd. Product name: KAYAHARD A-A. Liquid aromatic amine resin. Amine active hydrogen equivalent: 63.5 g / eq. - Silica #1: Silica with an average particle size of 0.4 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Silica #2: Silica with an average particle size of 0.4 μm, surface-treated with phenyltrimethoxysilane. - Silica #3: Silica with an average particle size of 0.4 μm, surface-treated with 3-glycidoxypropyltrimethoxysilane. - Silica #4: Silica with an average particle size of 0.4 μm, surface-treated with 3-methacryloxypropyltrimethoxysilane. - Silica #5: Silica with an average particle size of 0.7 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Silica #6: Silica with an average particle size of 1.0 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Silica #7: A mixture of bisphenol F-type epoxy resin with an epoxy equivalent of 160 and silica with an average particle size of 10 nm, manufactured by Admatechs Co., Ltd. Product name: YA-010A-JER. Silica concentration: 25% by mass. - Rubber particles #1: Manufactured by Kaneka Corporation. Product name: MX-139. A mixture of a bisphenol F type epoxy resin with an epoxy equivalent of 160 and core-shell type rubber particles with polybutadiene rubber as the core. Concentration of rubber particles: 33% by mass. - Rubber particles #2: Manufactured by Kaneka Corporation. Product name: MX-965. A mixture of a bisphenol F type epoxy resin with an epoxy equivalent of 160 and core-shell type rubber particles with silicone rubber as the core. Concentration of rubber particles: 25% by mass. - Organic phosphorus compound: Triphenylphosphine. - Aluminum complex: Manufactured by Kawaken Fine Chemicals Co., Ltd. Product name: Aluminum chelate A. Aluminum tris(acetylacetonate). - Coupling agent: Manufactured by Momentive Performance Materials Japan G.K. Product name: SILQUEST A-187 SILANE. 3-Glycidoxypropyltrimethoxysilane.

[0110] 2. Evaluation The following evaluations were conducted on the composition. The results are shown in Tables 1 to 3.

[0111] (1) Viscosity at 25°C The viscosity of the composition at 25°C was measured using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., model TVB-10H) under the condition of a rotational speed of 20 rpm.

[0112] (2) Glass transition temperature The composition was cured by heating at 100°C for 2 hours and then at 165°C for 2 hours to prepare an evaluation sample with dimensions of 5 mm × 50 mm × 2 mm.

[0113] The glass transition temperature of this sample was measured using a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Corporation, model number: DMA7100) under the conditions of a two-point bending mode, a frequency of 10 Hz, and a heating rate of 10°C / min.

[0114] (3) Viscosity at 110°C The temperature dependence of the viscosity of the composition was measured using a rheometer (Anton Paar, model number: MCR-102) under the conditions of a rotation speed of 1 rpm, a gap of 300 μm, and a heating rate of 5 °C / min. From the results, the viscosity of the composition at 110 °C was read.

[0115] When this viscosity is 0.35 Pa·s or less, it can be evaluated that the fluidity during heating of the composition is good, and when it is 0.25 Pa·s or less, it can be evaluated that the fluidity during heating of the composition is particularly good.

[0116] (4) Crack resistance 10 mg of the composition was applied in an X shape on a silicon substrate with dimensions of 25 mm × 25 mm × 775 μm. A silicon substrate with dimensions of 7 mm × 7 mm × 775 μm was placed on top of the applied composition. In this state, the silicon substrate and the composition were heated at 80 °C for 60 seconds and then cooled to 25 °C. As a result, the composition spread and wet between the two silicon substrates, and a fillet of the composition protruded from the outer periphery of the silicon substrate with dimensions of 7 mm × 7 mm × 775 μm. The silicon substrate and the composition were heated at 100 °C for 2 hours and then at 165 °C for 2 hours to prepare a sample for evaluation. This sample was placed in a constant temperature bath at 175 °C for 500 hours, and then the appearance of the sample was evaluated. As a result, when the number of cracks in the cured product of the composition in the sample was 0 to 10, it was evaluated as "good", and when the number of cracks was 11 or more, it was evaluated as "bad".

[0117]

Table 1

[0118]

Table 2

[0119]

Table 3

Explanation of symbols

[0120] 1 Semiconductor device 2 Substrate 3 Semiconductor element 5 Sealing portion

Claims

1. An epoxy compound (A), A liquid aromatic amine compound (B), And an inorganic filler (C), and contains, The epoxy compound (A) contains a liquid epoxy compound (A1) and a solid epoxy compound (A2), The solid epoxy compound (A2) contains a solid epoxy resin (a) selected from the group consisting of an isocyanate-modified epoxy resin, a naphthalene-type epoxy resin, and a biphenyl-type epoxy resin, Having a viscosity at 25 °C of 400 Pa·s or less, A resin composition.

2. The liquid epoxy compound (A1) contains a liquid epoxy compound (A11) having an epoxy equivalent of 100 g / eq. or more, The resin composition according to Claim 1.

3. The amount of the solid epoxy compound (A2) is 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A), The resin composition according to Claim 1.

4. The inorganic filler (C) contains a first inorganic filler (C1) having an average particle diameter of more than 0.1 μm and 15 μm or less, And a second inorganic filler (C2) having an average particle diameter of 0.1 μm or less, The amount of the second inorganic filler (C2) is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first inorganic filler (C1), The resin composition according to Claim 1.

5. The first inorganic filler (C1) contains silica surface-treated with at least one selected from the group consisting of a phenylaminosilane compound, a phenylsilane compound, an epoxysilane compound, and a methacryl silane compound, The resin composition according to Claim 4.

6. The liquid epoxy compound (A1) contains a silicone-modified epoxy resin (b), The resin composition according to Claim 1.

7. The amount of the silicone-modified epoxy resin (b) is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A), The resin composition according to Claim 6.

8. Further containing rubber particles (D), The resin composition according to Claim 1.

9. The rubber particles (D) contain at least one of butadiene rubber particles and silicone rubber particles, The resin composition according to Claim 8.

10. Further containing an organic phosphorus compound (E), The resin composition according to Claim 1.

11. For semiconductor encapsulation, The resin composition according to Claim 1.

12. An underfill material The resin composition according to claim 1.

13. A semiconductor device comprising a substrate, a semiconductor element mounted on the substrate, and a sealing portion filled in a gap between the substrate and the semiconductor element. The sealing portion contains a cured product of the resin composition according to any one of claims 1 to 12. Semiconductor device.

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