Resin composition and semiconductor device

Abstract

The present disclosure provides a resin composition capable of improving the fluidity and storage stability of the resin composition and increasing the glass transition temperature of a cured product. The resin composition contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filling material (C), and an amidine silicate (D) represented by formula (1). R1 and R2 are each independently hydrogen or a C1-C5 aliphatic hydrocarbon group, R3 and R4 are each independently a phenylene group or a naphthylene group, and R5 is at least one group selected from the group consisting of a phenyl group and groups represented by –CnH2n-X. n is 3-8. X is –SH, -NH2, -NH-Ph, -Ph-CH=CH2, -NH-C2H4-NH2, -N=C=O, a glycidyl ether group, or a group represented by formula (3). The viscosity of the resin composition at 25ºC is at most 400 Pa∙s.

Description

Resin composition and semiconductor device

[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 an encapsulant made from the resin composition.

[0002] Patent Document 1 discloses a liquid encapsulant that has both low thermal expansion and is easily injected into the gap between a semiconductor element and a substrate, and an electronic component in which the encapsulated portion is encapsulated using the liquid encapsulant.

[0003] Patent Document 1 discloses that the liquid sealant contains a liquid epoxy resin, a curing agent, a silica filler having an average particle size of 7 to 50 nm that has been surface-treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, a silica filler having an average particle size of 0.2 to 5 μm, and a Lewis base or a salt thereof, wherein the curing agent is an aromatic polyamine, the Lewis base or a salt thereof is triphenylphosphine, the total content of the silica filler is 45 to 77 parts by mass relative to 100 parts by mass of all components of the liquid sealant, and the mass ratio of the silica filler having an average particle size of 7 to 50 nm to the silica filler having an average particle size of 0.2 to 5 μm is 1:17.7 to 1:76.

[0004] Special Publication No. 2008-530321

[0005] An object of the present disclosure is to provide a resin composition that can improve the fluidity and storage stability of the resin composition and can increase the glass transition temperature of the cured product, and a semiconductor device that includes an encapsulating part that includes a cured product of this resin composition.

[0006] A resin composition according to one embodiment of the present disclosure contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an amidine silicate (D) represented by the following formula (1):

[0007]

[0008] In formula (1), R １ and R ２ are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; R ３ and R４ are each independently a phenylene group or a naphthylene group, R ５ is at least one group selected from the group consisting of a phenyl group and a group represented by the following formula (2):

[0009] -C ｎ H ２ｎ −X (2) In formula (2), n is 3 or more and 8 or less.

[0010] In formula (2), X is —SH, —NH ２ , -NH-Ph, -Ph-CH=CH ２ , —NH—C ２ H ４ -NH ２ , —N═C═O, a glycidyl ether group, or a group represented by the following formula (3):

[0011]

[0012] The viscosity of the resin composition at 25°C is 400 Pa·s or less.

[0013] 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 filling a gap between the substrate and the semiconductor, the sealing portion including a cured product of the resin composition.

[0014] FIG. 1 is a cross-sectional view of a semiconductor device according to an embodiment of the present disclosure.

[0015] 1. Overview An embodiment of the present disclosure will be described. Note that the following embodiments are merely a portion of various embodiments of the present disclosure. Furthermore, the following embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. The figures referred to below are schematic diagrams, and the dimensional ratios of the components in the figures do not necessarily reflect the actual dimensional ratios. Although the mechanism of action in the embodiments may be described below, this description of the mechanism of action includes an explanation based on speculation, and the present disclosure is not bound by the description of the mechanism of action.

[0016] A resin composition of an embodiment (hereinafter also referred to as composition (X)) contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an amidine silicate (D) represented by the following formula (1):

[0017]

[0018] In formula (1), R １ and R ２ are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; R ３ and R ４ are each independently a phenylene group or a naphthylene group, R ５ is at least one group selected from the group consisting of a phenyl group and a group represented by the following formula (2):

[0019] -C ｎ H ２ｎ −X (2) In formula (2), n is 3 or more and 8 or less.

[0020] In formula (2), X is —SH, —NH ２ , -NH-Ph, -Ph-CH=CH ２ , —NH—C ２ H ４ -NH ２ , —N═C═O, a glycidyl ether group, or a group represented by the following formula (3): “-Ph” is a phenyl group and “-Ph-” is a phenylene group.

[0021]

[0022] The viscosity of the resin composition at 25°C is 400 Pa·s or less.

[0023] According to the embodiment, the fluidity and storage stability of the resin composition can be improved, and the glass transition temperature of the cured product can be increased, so that the cured product can have good heat resistance.

[0024] The composition (X) can be used to produce a semiconductor device. More specifically, the composition (X) can be used to produce a sealing portion included in the semiconductor device. In particular, the composition (X) can be suitably used to produce a sealing portion where a semiconductor element is filled into a substrate when the semiconductor element is flip-chip mounted on the substrate. In other words, the composition (X) can be suitably used as an underfill material.

[0025] The use of the composition (X) is not limited to the encapsulation of semiconductor elements, but the composition (X) can be used for various purposes other than the encapsulation of semiconductor elements.

[0026] The embodiments will be described in more detail below.

[0027] 2. Composition As described above, the composition (X) contains the liquid epoxy compound (A), the liquid aromatic amine compound (B), the inorganic filler (C), and the amidine silicate (D).

[0028] As described above, the epoxy compound (A) is liquid. Liquid means that the epoxy compound (A) has fluidity at 25°C. All components contained in the epoxy compound (A) may be liquid, or the epoxy compound (A) may contain liquid components and solid components, and the epoxy compound (A) may be liquid as a whole by mixing the components. The liquid epoxy compound (A) can impart fluidity to the composition (X).

[0029] The viscosity of the epoxy compound (A) at 25°C is preferably 100 Pa s or less. A viscosity of 50 Pa s or less is more preferable, and a viscosity of 20 Pa s or less is even more preferable. The viscosity of the epoxy compound (A) at 25°C is, for example, 0.01 Pa s or more. A viscosity of 0.02 Pa s or more is even more preferable.

[0030] The epoxy compound (A) preferably contains a compound having two or more epoxy groups in one molecule. In this case, the reactivity of the epoxy compound (A) with 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 improved.

[0031] The epoxy compound (A) contains at least one selected from the group consisting of, for example, diglycidyl ether type epoxy resins such as p-aminophenol type epoxy resins, naphthalene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, and hydrogenated bisphenol A type epoxy resins; epoxy resins obtained by epoxidizing novolak resins obtained by reacting phenols with aldehydes, such as orthocresol novolak type epoxy resins; glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidylamine type epoxy resins obtained by reacting amine compounds such as aminodiphenylmethane and isocyanuric acid with epichlorohydrin; and silicone-modified epoxy resins (a1).

[0032] The epoxy compound (A) preferably contains a silicone-modified epoxy resin (a1). In this case, the fluidity of the composition (X) can be further enhanced. 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 thought 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 flexibly modifies the molecular chain of the silicone-modified epoxy resin (a1), thereby lowering the viscosity of the composition (X).

[0033] When the epoxy compound (A) contains a silicone-modified epoxy resin (a1), the proportion of the silicone-modified epoxy resin (a1) relative to the epoxy compound (A) is preferably 5% by mass or more and 30% by mass or less. When this proportion is 5% by mass or more, the fluidity of the composition (X) can be further increased. When this proportion is 7% by mass or more, more preferably 10% by mass or more. When this proportion is 30% by mass or less, there is an advantage that weight loss when the composition (X) is heated and cured can be further suppressed. When this proportion is 25% by mass or less, more preferably 20% by mass or less.

[0034] It is also preferred that the epoxy compound (A) contains at least one selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, p-aminophenol epoxy resins, and naphthalene epoxy resins, in which case the curability of the composition (X) can be particularly enhanced.

[0035] The epoxy compound (A) may contain a commercially available product. For example, the epoxy compound (A) may contain at least one selected from the group consisting of bisphenol F epoxy resin (product name: YDF-8170C, epoxy equivalent: 155 to 165 g / eq) manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol A epoxy resin (product name: YD-128, epoxy equivalent: 184 to 194 g / eq) manufactured by Nippon Steel Chemical & Material Co., Ltd., and multifunctional epoxy resin (product name: jER-630, epoxy equivalent: 90 to 105 g / eq) manufactured by Mitsubishi Chemical Corporation.

[0036] The epoxy equivalent of the epoxy compound (A) is, for example, 40 g / eq. or more and 1000 g / eq. or less. In this case, the reactivity of the epoxy compound (A) with the aromatic amine (B) can be enhanced. The epoxy equivalent of the epoxy compound (A) is preferably 50 g / eq. or more. The epoxy equivalent of the epoxy compound (A) is preferably 300 g / eq. or less.

[0037] As described above, the aromatic amine (B) is liquid. All components contained in the aromatic amine (B) may be liquid, or the aromatic amine (B) may contain liquid components and solid components, and the aromatic amine (B) may be liquid as a whole by mixing the components. The liquid aromatic amine (B) can impart fluidity to the composition (X).

[0038] The aromatic amine (B) preferably contains an aromatic amine (C1) having two or more amino groups per molecule. In this case, the reactivity of the epoxy compound (A) with 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.

[0039] Examples of the aromatic amine (B) include 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, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenediamine, and the like. The compound contains at least one member selected from the group consisting of aromatic amines having two aromatic rings, such as bis(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, and reaction products of aromatic diamines and styrene.

[0040] It is particularly preferable that the aromatic amine (B) contains at least one of diethyltoluenediamine and dimethylthiotoluenediamine, in which case the storage stability of the composition (X) can be further improved.

[0041] The aromatic amine (B) may contain a commercially available product. For example, the aromatic amine (B) may contain at least one selected from the group consisting of an amine curing agent manufactured by Nippon Kayaku Co., Ltd. (product name: KAYAHARD AA, amine active hydrogen equivalent: 63.5 g / eq) and a modified aromatic amine curing agent manufactured by ADEKA Corporation (product name: EH-105L, amine active hydrogen equivalent: 61 g / eq).

[0042] 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 mole of amine active hydrogen. The amine active hydrogen equivalent of the aromatic amine (B) is, for example, preferably 30 g / eq. or more. The amine active hydrogen equivalent of the aromatic amine (B) is, for example, preferably 100 g / eq. or less.

[0043] 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. This allows the glass transition temperature of the cured product to be appropriately increased, and the crack resistance of the cured product to be improved. This equivalent ratio is more preferably 0.7 or more, and even more preferably 0.8 or more. It is also more preferable that this equivalent ratio is 1.3 or less.

[0044] The inorganic filler (C) can contribute to a low linear expansion coefficient of the cured product, thereby contributing to suppressing warpage and breakage of the semiconductor device. The inorganic filler (C) can also contribute to improving the thermal conductivity of the cured product, thereby increasing the heat dissipation ability of the semiconductor device.

[0045] The inorganic filler (C) may contain 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, calcined clay, uncalcined 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.

[0046] The inorganic filler (C) preferably contains silica, which can particularly contribute to increasing the elasticity, decreasing the linear expansion coefficient, and decreasing the dielectric loss tangent of the cured product.

[0047] The particle shape of the inorganic filler (C) is not particularly limited and may be crushed, needle-like, scaly, spherical, etc. In order to improve the dispersibility of the inorganic filler (C) in the composition (X) and to control the viscosity of the composition (X), the particle shape of the inorganic filler (C) is preferably spherical.

[0048] The particles of the inorganic filler (C) are preferably surface-treated with a surface treatment agent. In this case, the dispersibility of the inorganic filler (C) in the composition (X) can be improved. This can suppress a decrease in the fluidity of the composition (X) due to the inorganic filler (C). 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.

[0049] The silane-based compound contains at least one selected from the group consisting of, for example, a silane compound having an amino group, an epoxy silane, a mercapto silane, an alkyl silane, a ureido silane, and a vinyl silane.

[0050] Specifically, examples of the silane-based compound include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylmethyldimethoxysilane. thoxysilane, 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-di 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) The compound contains at least one selected from the group consisting of anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane.

[0051] 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. The average particle diameter of the inorganic filler (C) is more preferably 0.3 μm or more. It is also more preferably 20 μm or less. The average particle diameter is a volume-based median diameter calculated from the particle size distribution measured by a laser diffraction / scattering method, and can be measured using a commercially available laser diffraction / scattering particle size distribution measuring device.

[0052] The inorganic filler (C) preferably contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm and a second inorganic filler (C2) having an average particle size of not more than 0.1 μm. In this case, an increase in viscosity of the composition (X) due to the inorganic filler (C) can be further suppressed. This allows the composition (X) to have better fluidity.

[0053] The average particle size of the first inorganic filler (C1) is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The average particle size of the first inorganic filler (C1) is more preferably 5 μm or less, and more preferably 2 μm or less. The average particle size of the second inorganic filler (C2) is more preferably 5 nm or more, and more preferably 10 nm or more. The average particle size of the second inorganic filler (C2) is more preferably 80 nm or less, and more preferably 60 nm or less.

[0054] When the inorganic filler (C) contains a first inorganic filler (C1) and a 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 per 100 parts by mass of the first inorganic filler (C1). In this case, the increase in 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.

[0055] The first inorganic filler (C1) may contain silica or may contain only silica, and the second inorganic filler (C2) may also contain silica or may contain only silica.

[0056] It is particularly preferred 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 methacrylsilane compounds. In this case, the fluidity of composition (X) can be further improved, and the storage stability of composition (X) can be further enhanced. In composition (X) containing (C) and inorganic filler (C), if inorganic filler (C) is treated with a surface treatment agent, storage stability may be reduced. However, if the first inorganic filler (C1) contains silica surface-treated with any of the above-mentioned silane compounds, the reduction in storage stability of composition (X) can be suppressed. Examples of phenylaminosilane compounds include N-phenyl-3-aminopropyltrimethoxysilane, etc. Examples of phenylsilane compounds include phenyltrimethoxysilane, etc. The epoxy silane compound contains at least one compound 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 compound selected from the group consisting of, for example, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.

[0057] The total proportion of the first inorganic filler (C1) and the second inorganic filler (C2) relative to the inorganic filler (C) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. The inorganic filler (C) may contain only the first inorganic filler (C1) and the second inorganic filler (C2).

[0058] The proportion of the inorganic filler (C) is preferably 40% by mass or more and 80% by mass or less relative to 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. This can improve the crack resistance of the cured product of the composition (X). 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.

[0059] The amidine silicate (D) can suppress an increase in viscosity of the composition (X) and can improve the storage stability of the composition (X). Furthermore, the amidine silicate (D) is less likely to cause a decrease in the glass transition temperature of the cured product, and therefore the decrease in the glass transition temperature of the cured product can be suppressed or the glass transition temperature can be improved.

[0060] The mechanism by which amidine silicate (D) achieves the above-mentioned effect is not clear, but is speculated as follows. It is believed that amidine silicate (D) inhibits the progress of the reaction between the epoxy compound (A) and the aromatic amine compound (B), thereby inhibiting the increase in viscosity of the composition (X) due to the reaction between the epoxy compound (A) and the aromatic amine compound (B) at room temperature. In addition, it is believed that the amidine silicate (D) acts on the surface of the inorganic filler (C) particles, thereby inhibiting the hydroxyl groups on the particle surface from reacting with the epoxy compound (A), etc., which also inhibits the increase in viscosity of the composition (X). It is also believed that the amidine silicate (D) acts on the surface of the inorganic filler (C) particles, thereby reducing friction on the particle surface, which can reduce the viscosity of the composition (X).

[0061] In addition, organic phosphorus compounds such as triphenylphosphine can also have the effect of inhibiting the reaction between the epoxy compound (A) and the aromatic amine compound (B), but the organic phosphorus compounds can lower the glass transition temperature of the cured product. This is thought to be because the organic phosphorus compounds reduce the epoxy group of the epoxy compound (A), thereby lowering the crosslink density of the cured product. However, amidine silicate (D) does not have the effect of reducing the epoxy group, and therefore is thought to be less likely to lower the glass transition temperature of the cured product. Therefore, the cured product can have good heat resistance.

[0062] As described above, the amidine silicate (D) has a structure represented by the following formula (1).

[0063]

[0064] In formula (1), R １ and R ２ are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Therefore, there is an advantage that the amidine silicate (D) inhibits homopolymerization of the epoxy compound (A) during storage of the composition (X), thereby improving the storage stability of the composition (X). This is because R １ and R ２ However, this is thought to be because the basicity and nucleophilicity of the nitrogen moiety can be kept relatively small. １ and R ２ Each of the above is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably an aliphatic hydrocarbon group having 1 to 2 carbon atoms.

[0065] In formula (1), R ３ and R ４ are each independently a phenylene group or a naphthylene group. Therefore, even when the composition (X) is stored at a relatively high temperature, the amidine silicate (D) can improve the storage stability of the composition (X) and can reduce the viscosity of the composition (X) during storage at a high temperature. This is thought to be because the phenylene group or naphthylene group tends to give the compound of formula (1) a high melting point, and therefore tends to exhibit the effect of suppressing the homopolymerization of the epoxy compound (A) even at a high temperature.

[0066] R ５ is at least one group selected from the group consisting of a phenyl group and a group represented by the following formula (2):

[0067] -C ｎ H ２ｎ -X (2) In formula (2), n is 3 or more and 8 or less. In formula (2), X is -SH, -NH ２ , -NH-Ph, -Ph-CH=CH ２ , —NH—C ２ H ４ -NH ２ , —N═C═O, a glycidyl ether group, or a group represented by the following formula (3):

[0068]

[0069] R ５ By having the above structure, it is possible to improve storage stability even at high temperatures, and there is an advantage that the viscosity can be reduced even at high temperatures. This is thought to be because the amidine silicate (D) is likely to have a high melting point due to the phenyl group or the group represented by formula (2), and therefore the above effect is likely to be exhibited even at high temperatures. ５ has a structure shown in formula (2), X in formula (2) is -SH, -NH ２ , -NH-Ph, -Ph-CH=CH ２ , —NH—C ２ H ４ -NH ２ , —N═C═O, a glycidyl ether group, or a group represented by formula (3) has the advantage of easily increasing the adhesive strength of the cured product. This is thought to be because the functional group can form a chemical bond with the surface of the adherend. ５ It is more preferable that the structure is a phenyl group. In this case, there is an advantage that the storage stability and flowability of the composition (X) can be more easily improved.

[0070] The ratio of amidine silicate (D) to composition (X) is preferably 0.03% by mass or more and 1.0% by mass or less. If this ratio is 0.03% by mass or more, the viscosity of composition (X) at high temperatures can be reduced, the storage stability of composition (X) is further improved, and a decrease in the glass transition temperature of the cured product is less likely to occur. If this ratio 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 this ratio is 1.0% by mass or less, there is an advantage that the viscosity of composition (X) at 25°C is less likely to increase. If this ratio is 0.8% by mass or less, it is more preferable, and if it is 0.5% by mass or less, it is even more preferable.

[0071] The composition (X) may or may not contain an organic phosphorus compound such as triphenylphosphine. When the composition (X) contains an organic phosphorus compound, the content of the organic phosphorus compound is preferably set so as not to excessively lower the glass transition temperature of the cured product. When the composition (X) contains an organic phosphorus compound, the ratio of the organic phosphorus compound to the composition (X) is preferably 0.3 mass% or less, and more preferably 0.2 mass% or less.

[0072] The composition (X) may contain rubber particles (E). When the composition (X) contains the rubber particles (E), the crack resistance of the cured product can be improved.

[0073] The rubber particles (E) are preferably core-shell type rubber particles. In this case, the crack resistance of the cured product can be further improved. The rubber particles (E) preferably contain at least one of silicone rubber particles and butadiene rubber particles. In this case, the crack resistance of the cured product can be further improved.

[0074] The silicone rubber particles may include, but are not limited to, silicone-based core-shell particles (core-shell type rubber particles), specifically, commercially available products such as Kane Ace (registered trademark) MX-962 manufactured by Kaneka Corporation. The butadiene rubber particles may include, but are not limited to, butadiene-based core-shell particles (core-shell type rubber particles), specifically, commercially available products such as Kane Ace (registered trademark) MX-136 manufactured by Kaneka Corporation.

[0075] The ratio of rubber particles (E) to composition (X) is preferably 0.1% by mass or more and 3.0% by mass or less. If the ratio is 0.1% by mass or more, the crack resistance of the cured product can be particularly improved. If this ratio 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. If the ratio of rubber particles (E) is 3.0% by mass or less, there is an advantage that the viscosity of composition (X) is less likely to increase. If this ratio 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.

[0076] The composition (X) may contain an aluminum complex (F). When the composition (X) contains an aluminum complex (F), the fluidity of the composition (X) can be further increased.

[0077] The aluminum complex (F) contains at least one selected from the group consisting of, for example, aluminum trisacetylacetonate and aluminum bisethylacetoacetate monoacetylacetonate.

[0078] The amount of aluminum complex (F) relative to 100 parts by mass of the total of epoxy compound (A) and aromatic amine compound (B) is preferably 0.03 parts by mass or more and 0.30 parts by mass or less. If this amount is 0.03 parts by mass or more, the fluidity of composition (X) can be further improved. If this amount is 0.05 parts by mass or more, it is more preferable, and if it is 0.10 parts by mass or more, it is even more preferable. If the amount of aluminum complex (F) is 0.30 parts by mass or less, there is an advantage that deterioration of the storage stability of composition (X) can be suppressed. If this amount is 0.25 parts by mass or less, it is more preferable, and if it is 0.20 parts by mass or less, it is even more preferable.

[0079] The composition (X) may contain additives other than the above components, if necessary. The additives are preferably contained in an amount that does not excessively impair the above-mentioned properties of the composition (X) and the curing agent.

[0080] The additive may include at least one selected from the group consisting of, for example, a resin modifier, an antioxidant, a curing aid, a coupling agent, a colorant, a thixotropic agent, an ion trapping agent, an antifoaming agent, a leveling agent, and an antioxidant.

[0081] It is preferred that the composition (X) contains no solvent or only a trace amount of solvent that is unavoidably mixed in.

[0082] The viscosity of composition (X) at 25°C is 400 Pa·s or less. Therefore, composition (X) can have good fluidity during molding. This viscosity is more preferably 200 Pa·s or less, and even more preferably 100 Pa·s or less. Furthermore, the viscosity of composition (X) at 25°C may be, for example, 0.01 Pa·s or more, or even 0.02 Pa·s or more. This viscosity of composition (X) can be achieved by appropriately setting the composition of composition (X) within the range described above. The method for measuring viscosity will be explained in the Examples section.

[0083] The glass transition temperature of the cured product of 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. The glass transition temperature is, for example, 180°C or lower. The method for measuring the glass transition temperature will be explained in the Examples section.

[0084] 1 shows an example of a semiconductor device 1. The composition (X) in this embodiment is for semiconductor encapsulation. That is, the encapsulation portion 5 in the semiconductor device 1 can be produced from the composition (X). The encapsulation portion 5 is a component that protects the semiconductor element 3 in the semiconductor device 1 by covering a part or all of the semiconductor element 3.

[0085] Composition (X) can be used as an underfill material. The underfill material is a material for producing a sealing portion 5 that fills the gap between a substrate 2 and a semiconductor element 3 surface-mounted on the substrate 2. That is, in this case, the semiconductor device 1 includes a substrate 2, a semiconductor element 3 mounted on the substrate 2, and a sealing portion 5 that fills the gap between the substrate 2 and the semiconductor element 3, and the sealing portion 5 includes a cured product of composition (X).

[0086] The substrate 2 includes an insulating substrate such as a glass epoxy substrate, a polyimide substrate, a polyester substrate, or a ceramic substrate, and conductive wiring 21 overlaid on the insulating substrate. The conductive wiring 21 includes, for example, electrode pads. The substrate 2 is, for example, a motherboard, a package substrate, or an interposer substrate.

[0087] The semiconductor element 3 may be any suitable surface-mount type element. The semiconductor element 3 has 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 may be a flip-chip type chip such as a BGA (ball grid array), an LGA (land grid array), or a CSP (chip-size package). The semiconductor element 3 may also be a PoP (package-on-package) type chip.

[0088] A semiconductor element 3 is surface-mounted on the substrate 2. More specifically, the surface of the semiconductor element 3 having bump electrodes 31 faces the substrate 2, the bump electrodes 31 on the semiconductor element 3 are joined to the electrode pads of the conductor wiring 21 on the substrate 2 by solder bumps 4, and the bump electrodes 31 are electrically connected to the electrode pads by the solder bumps 4. Note that the manner of connection between the semiconductor element 3 and the substrate 2 is not limited to the above, as long as the semiconductor element 3 is mounted on the substrate 2 so that a gap is left between the semiconductor element 3 and the substrate 2.

[0089] The sealing portion 5 fills the gap between the semiconductor element 3 and the substrate 2 , so that the bump electrodes 31 , the solder bumps 4 and the electrode pads of the conductor wiring 21 are embedded in the sealing portion 5 .

[0090] In the embodiment, the composition (X) may have a high glass transition temperature, and therefore the semiconductor device 1 may have high heat resistance.

[0091] An example of a method for manufacturing the semiconductor device 1 will now be described. First, the substrate 2, the semiconductor element 3, and the composition (X) are prepared.

[0092] A semiconductor element 3 is surface-mounted on a substrate 2. Specifically, the surface of the semiconductor element 3 having the bump electrodes 31 is placed opposite the substrate 2, and solder bumps 4 are interposed between the bump electrodes 31 on the semiconductor element 3 and the electrode pads of the conductor wiring 21 on the substrate 2. The solder contained in the solder bumps 4 is a lead-free solder with 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 by an appropriate heating method such as reflow heating, and then solidified. The heating temperature is set appropriately depending on the solder bumps 4 so that the solder bumps 4 melt, but for example, the maximum heating temperature is 180°C or higher and 300°C or lower. As a result, 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.

[0093] Next, composition (X) is injected into the gap between the semiconductor element 3 and the substrate 2 using a dispenser or the like. Composition (X) flows through the gap between the semiconductor element 3 and the substrate 2 due to capillary action. When causing composition (X) to flow, the viscosity of composition (X) may be reduced by heating composition (X), if necessary. In this case, the heating temperature of composition (X) is, for example, 80°C or higher and 130°C or lower. As a result, composition (X) fills the gap between the semiconductor element 3 and the substrate 2. In this state, composition (X) is heated to harden it. The heating conditions in this case are appropriately set depending on the composition of composition (X), but for example, the heating temperature is 80°C or higher and 180°C or lower, and the heating time is 60 minutes or higher and 300 minutes or lower. As a result, a sealing portion 5 containing a cured product of composition (X) is produced in the gap between the semiconductor element 3 and the substrate 2.

[0094] In the embodiment, since the composition (X) can have high fluidity, it is possible to suppress the occurrence of unfilled portions of the composition (X) and the sealing portion 5 between the semiconductor element 3 and the substrate 2 .

[0095] The method for manufacturing the semiconductor device 1 is not limited to the above.

[0096] 4. Aspects A composition (X) according to a first aspect of the present disclosure contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an amidine silicate (D) represented by the following formula (1):

[0097]

[0098] In formula (1), R １ and R ２ are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; R ３ and R ４ are each independently a phenylene group or a naphthylene group, R ５ is at least one group selected from the group consisting of a phenyl group and a group represented by the following formula (2):

[0099] -C ｎ H ２ｎ -X (2) In formula (2), n is 3 or more and 8 or less. In formula (2), X is -SH, -NH ２ , -NH-Ph, -Ph-CH=CH ２ , —NH—C ２ H ４ -NH ２ , —N═C═O, a glycidyl ether group, or a group represented by the following formula (3):

[0100]

[0101] The viscosity of composition (X) at 25°C is 400 Pa·s or less.

[0102] According to this embodiment, the fluidity and storage stability of the resin composition can be improved, and the glass transition temperature of the cured product can be increased.

[0103] In a second aspect, the inorganic filler (C) of the first aspect contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm, and a second inorganic filler (C2) having an average particle size of 0.1 μm or less, and the amount of the second inorganic filler (C2) is 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the first inorganic filler (C1).

[0104] According to this embodiment, the fluidity of the resin composition can be further increased.

[0105] In a third aspect, in the first or second aspect, the first inorganic filler (C1) contains silica that has been surface-treated with at least one compound selected from the group consisting of a phenylaminosilane compound, a phenylsilane compound, an epoxysilane compound, and a methacrylsilane compound.

[0106] According to this embodiment, the fluidity and storage stability of the resin composition can be further improved.

[0107] In a fourth aspect, in any one of the first to third aspects, the epoxy compound (A) contains a silicone-modified epoxy resin (a1).

[0108] According to this embodiment, the fluidity of the resin composition can be further increased.

[0109] In a fifth aspect, in the fourth aspect, the proportion of the silicone-modified epoxy resin (a1) is 5% by mass or more and 30% by mass or less relative to the epoxy compound (A).

[0110] According to this embodiment, the fluidity of the resin composition can be further increased.

[0111] In a sixth aspect, in any one of the first to fifth aspects, the composition (X) further contains rubber particles (E).

[0112] According to this embodiment, the crack resistance of the cured product can be improved.

[0113] In a seventh aspect, in the sixth aspect, the rubber particles (E) contain core-shell type rubber particles.

[0114] According to this embodiment, the crack resistance of the cured product can be further improved.

[0115] In an eighth aspect, in any one of the first to seventh aspects, the composition (X) further contains an aluminum complex (F).

[0116] According to this embodiment, the fluidity of the composition can be further increased.

[0117] In a ninth aspect, in any one of the first to eighth aspects, the composition (X) is for semiconductor encapsulation.

[0118] In a tenth aspect, in any one of the first to ninth aspects, the composition (X) is an underfill material.

[0119] A semiconductor device (1) according to an eleventh aspect includes a substrate (2), a semiconductor element (3) mounted on the substrate (2), and a sealing portion (5) filling a gap between the substrate (2) and the semiconductor element (3). The sealing portion (5) contains a cured product of the resin composition according to any one of the first to tenth aspects.

[0120] Specific examples of the embodiments will be described below, but the present disclosure is not limited to these examples.

[0121] 1. Preparation of Compositions Compositions were prepared by mixing the components shown in the table. Details of the components in the table are as follows: - 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. - Epoxy compound #2: Manufactured by Momentive Performance Materials Japan, LLC. Product name: TSL9906. Liquid silicone-modified epoxy resin (siloxane oligomer with glycidoxypropyl groups at both ends). Epoxy equivalent: 181 g / eq. - Curing agent: 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: Manufactured by Admatechs Co., Ltd. Product name: YA-010A-JER. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 g / eq and silica with an average particle size of 10 nm. Silica concentration: 25% by mass. Amidine silicate: Amidine silicate having the structure shown in the formula:

[0122]

[0123] - Organophosphorus compound: triphenylphosphine. - Aluminum complex: manufactured by Kawaken Fine Chemicals Co., Ltd. Product name: Aluminum Chelate A. Aluminum tris(acetylacetonate). - Rubber particles #1: manufactured by Kaneka Corporation. Product name: MX-139. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 g / eq and core-shell rubber particles with a polybutadiene rubber core. Concentration of rubber particles: 33% by mass. - Rubber particles #2: manufactured by Kaneka Corporation. Product name: MX-965. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 and core-shell rubber particles with a silicone rubber core. Concentration of rubber particles: 25% by mass. - Coupling agent: manufactured by Momentive Performance Materials Japan, LLC. Product name: SILQUEST A-187 SILANE. 3-glycidoxypropyltrimethoxysilane.

[0124] 2. Evaluation The compositions were evaluated as follows, and the results are shown in the table below.

[0125] (1) Viscosity at 25° C. The viscosity of the composition at 25° C. was measured using a B-type rotational viscometer (TVB-10H, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm.

[0126] (2) Storage Stability The composition was subjected to a treatment of being exposed to a temperature of 40°C for 8 hours. The viscosity of the composition before this treatment (η0) and the viscosity of the composition after this treatment (η1) were measured using a B-type rotational viscometer (TVB-10H, manufactured by Toki Sangyo Co., Ltd.) at a temperature of 40°C and a rotation speed of 20 rpm. From these results, the viscosity increase ratio ((η1-η0) × 100 / η0) was calculated.

[0127] When this result is 100% or less, the storage stability can be evaluated as good, and when it is 50% or less, the storage stability can be evaluated as particularly good.

[0128] (3) Fluidity Two glass slides were placed facing each other with a gap of 50 μm between them, and the composition was poured between the glass slides at a temperature of 110° C. The composition was allowed to flow between the glass slides. The time from the start of pouring until the maximum movement distance of the composition between the glass slides reached 30 mm was measured.

[0129] If the result is 500 seconds or less, the fluidity can be evaluated as good, and if the result is 300 seconds or less, the fluidity can be evaluated as particularly good.

[0130] (4) Viscosity at 110°C The temperature dependence of the viscosity of the composition was measured using a rheometer (manufactured by Anton Paar, model number: MCR-102) under conditions of a rotation speed of 1 rpm, a gap of 300 μm, and a heating rate of 5°C / min, and the viscosity of the composition at 110°C was read from the results.

[0131] If this viscosity is 0.35 Pa·s or less, the composition can be evaluated as having good fluidity when heated, and if it is 0.25 Pa·s or less, the composition can be evaluated as having particularly good fluidity when heated.

[0132] (5) Bending Test The composition was molded, heated at 100°C for 2 hours, and then heated at 165°C for 2 hours to cure it, and an evaluation sample measuring 70 mm x 10 mm x 3 mm was prepared.

[0133] A bending test was carried out on this sample at a temperature of 25° C., with a support distance of 48 mm and a test speed of 1.5 mm / min. From the results, the bending strength, Young's modulus and bending strain of the sample were calculated.

[0134] With regard to bending strength, if it is 100 MPa or more, it can be evaluated that the reliability of a semiconductor device having a sealing part containing a cured product of the composition is good, and if it is 130 MPa or more, it can be evaluated that the reliability of the semiconductor device is particularly good.

[0135] With regard to Young's modulus, if it is 6 GPa or more and 14 GPa or less, it can be evaluated that the reliability of the semiconductor device is good, and if it is 7 GPa or more and 12 GPa or less, it can be evaluated that the reliability of the semiconductor device is particularly good.

[0136] With regard to bending strain, if it is 2.0% or more, it can be evaluated that the reliability of the semiconductor device is good, and if it is 2.5% or more, it can be evaluated that the reliability of the semiconductor device is particularly good.

[0137] (6) Glass Transition Temperature The composition was molded, heated at 100°C for 2 hours, and then heated at 165°C for 2 hours to cure it, and a sample for evaluation measuring 5 mm x 50 mm x 2 mm was prepared.

[0138] 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 conditions of a double-support bending mode, a frequency of 10 Hz, and a temperature rise rate of 10° C. / min.

[0139]

[0140]

[0141] REFERENCE SIGNS LIST 1 semiconductor device 2 substrate 3 semiconductor element 5 sealing portion

Claims

1. A liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an amidine silicate (D) represented by the following formula (1), In formula (1), R １ and R ２ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; R ３ and R ４ each independently represents a phenylene group or a naphthylene group; R ５ is at least one group selected from the group consisting of a phenyl group and a group represented by the following formula (2), ｎ H ２ｎ -X (2) In formula (2), n is 3 or more and 8 or less, and in formula (2), X is -SH, -NH ２ , -NH-Ph, -Ph-CH=CH ２ , -NH-C ２ H ４ -NH ２ , —N═C═O, a glycidyl ether group, or a group represented by the following formula (3): A resin composition having a viscosity of 400 Pa·s or less at 25°C.

2. The resin composition according to claim 1, wherein the inorganic filler (C) contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm, and a second inorganic filler (C2) having an average particle size of 0.1 μm or less, and the amount of the second inorganic filler (C2) is 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the first inorganic filler (C1).

3. The resin composition according to claim 2, wherein the first inorganic filler (C1) contains silica that has been surface-treated with at least one compound selected from the group consisting of a phenylaminosilane compound, a phenylsilane compound, an epoxysilane compound, and a methacrylsilane compound.

4. The resin composition according to claim 1, wherein the epoxy compound (A) contains a silicone-modified epoxy resin (a1).

5. The resin composition according to claim 4, wherein the ratio of the silicone modified epoxy resin (a1) is 5% by mass or more and 30% by mass or less relative to the epoxy compound (A).

6. The resin composition according to claim 1, further comprising rubber particles (E).

7. The resin composition according to claim 6, wherein the rubber particles (E) contain core-shell type rubber particles.

8. The resin composition according to claim 1, further comprising an aluminum complex (F).

9. The resin composition according to claim 1, which is used for semiconductor encapsulation.

10. The resin composition according to claim 1, which is an underfill material.

11. A semiconductor device comprising: a substrate; a semiconductor element mounted on the substrate; and a sealing portion filling a gap between the substrate and the semiconductor element, the sealing portion comprising a cured product of a resin composition according to any one of claims 1 to 10.