Epoxy resin composition, cured product, and semiconductor device

Abstract

To provide an epoxy resin composition having a low tendency for creeping and a long pot life.SOLUTION: An epoxy resin composition comprises: an epoxy resin (A); an aromatic amine compound (B); and dicyandiamide (C). The content of dicyandiamide (C) is 0.001 mass% to 0.1 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition. More specifically, it relates to an epoxy resin composition for semiconductor encapsulation, a cured product, a semiconductor device, and a method for manufacturing a semiconductor device.

Background Art

[0002] There is a flip chip mounting technique in the technology of mounting a semiconductor chip on a wiring board. Flip chip mounting is a mounting method in which protruding electrodes (bumps) are formed on the surface of a semiconductor chip, the surface on which the bumps are formed is oriented toward the wiring board, and the semiconductor chip and the wiring board are directly connected via the bumps. For the purpose of protecting the connected semiconductor chip, wiring board, and the bumps existing between them (gap), an underfill is filled into the gap and cured to manufacture a semiconductor component.

[0003] When filling the underfill into the gap, a phenomenon (creeping) may occur in which the resin component of the underfill climbs up the back surface of the surface of the semiconductor chip where the bumps are formed. As a method for preventing the occurrence of creeping, performing a treatment on the surface of the semiconductor chip (i.e., the above-mentioned back surface) to repel the creeping component (Patent Document 1), blending a silicone-based additive into the underfill (Patent Document 2), etc. are known.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, even the underfills disclosed in these patent documents were insufficient from the viewpoint of suppressing creeping. There was also a problem that the viscosity increased due to the progress of the curing reaction over time, and the performance as an underfill deteriorated over time (i.e., the pot life was short).

[0006] Therefore, an object of the present invention is to provide an epoxy resin composition in which creeping hardly occurs and the pot life is long. Another object is to provide a cured product of the above epoxy resin composition, a semiconductor device including the cured product, and a method for manufacturing the semiconductor device.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above object, the present inventors have found that the problems can be solved by using a composition having a specific configuration. The present invention has been completed based on these findings.

[0008] That is, in the present invention, an epoxy resin (A), an aromatic amine compound (B), and dicyandiamide (C), and an epoxy resin composition containing the same, wherein the content of dicyandiamide (C) is 0.001 to 0.1% by mass, is provided.

[0009] The epoxy resin composition of the present invention preferably further contains a polyether-modified polydimethylsiloxane (D).

[0010] In the epoxy resin composition of the present invention, the content of the polyether-modified polydimethylsiloxane (D) is preferably 0.0001 to 0.1% by mass.

[0011] In the epoxy resin composition of the present invention, the content of dicyandiamide (C) is preferably 0.001 to 0.049% by mass.

[0012] The epoxy resin composition of the present invention preferably has a viscosity of 2000 mPa·s or less for the epoxy resin (A) and / or the aromatic amine compound (B).

[0013] The epoxy resin composition of the present invention further contains an inorganic filler (E), and preferably has a content of the inorganic filler (E) of 40 to 80% by mass.

[0014] The epoxy resin composition of the present invention preferably further contains an elastomer (F).

[0015] The epoxy resin composition of the present invention preferably further contains a coupling agent (K).

[0016] The epoxy resin composition of the present invention preferably further contains a pigment (H).

[0017] The epoxy resin composition of the present invention is preferably for semiconductor encapsulation.

[0018] The epoxy resin composition of the present invention is preferably an underfill.

[0019] The present invention also provides a cured product of the above epoxy resin composition.

[0020] In the present invention, a substrate, a semiconductor element disposed on the substrate, and the cured product for encapsulating the semiconductor element, and a semiconductor device including the same are provided.

[0021] In the present invention, a step of filling a gap between a substrate and a semiconductor element disposed on the substrate with the epoxy resin composition, and a step of heating and curing the epoxy resin composition, and a method for manufacturing a semiconductor device including the same are provided.

Advantages of the Invention

[0022] The epoxy resin composition of the present invention is less likely to experience creep and has a long pot life. Therefore, a semiconductor device including a cured product of the epoxy resin composition exhibits high reliability.

Embodiments for Carrying Out the Invention

[0023] (Epoxy resin composition) The epoxy resin composition of the present invention contains an epoxy resin (A), an aromatic amine compound (B), and dicyandiamide (C), and is characterized in that the content of dicyandiamide (C) is 0.001 to 0.1% by mass. The epoxy resin composition may further contain any one or more of polyether-modified polydimethylsiloxane (D) (hereinafter referred to as "siloxane (D)"), an inorganic filler (E), an elastomer (F), a coupling agent (G), a pigment (H), a dispersant (I), a curing agent (J), and a curing accelerator (K).

[0024] ·Epoxy resin (A) By including the epoxy resin (A), the epoxy resin composition can form a cured product having high electrical insulation. The number of epoxy groups in the epoxy resin (A) is not particularly limited as long as it is 1 or more, but it is preferably 2 or more (that is, it is a polyfunctional type epoxy resin). The epoxy resin (A) can be used alone or in combination of two or more.

[0025] The epoxy resin (A) may be liquid or solid at room temperature (25°C), but is preferably liquid from the viewpoint of the solubility of dicyandiamide (C). Even if it is a solid epoxy resin, it can be preferably used when it shows a liquid state as a mixture by being used in combination with a liquid epoxy resin.

[0026] When the epoxy resin (A) is liquid at 25°C, its viscosity is not particularly limited. For example, it is preferably 5000 mPa·s or less, more preferably 3000 mPa·s or less, and still more preferably 2000 mPa·s or less. Also, for example, it is preferably 1 mPa·s or more, more preferably 10 mPa·s or more. When the viscosity of the epoxy resin (A) is within the above range, the solubility of dicyandiamide (C) is improved, so that even when the content of dicyandiamide (C) is small (i.e., 0.1 mass% or less), the effect of suppressing creeping by including this tends to be improved. The above viscosity can be measured, for example, as the viscosity when rotating at 50 rpm for 1 minute at a liquid temperature of 25°C using a Tokimec viscometer (model number: TVB-10M, manufactured by Toki Sangyo Co., Ltd.).

[0027] The epoxy resin (A) is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin, biphenol type epoxy resin, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin (glycidylamine type epoxy resin having no aromatic structure or glycidylamine type epoxy resin having an aromatic structure), glycidyl ester type epoxy resin (glycidyl ester type epoxy resin having no aromatic structure or glycidyl ester type epoxy resin having an aromatic structure), cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin (linear aliphatic epoxy resin having no aromatic structure or linear aliphatic epoxy resin having an aromatic structure), epoxy resin having a butadiene structure (epoxy resin having a butadiene structure having no aromatic structure or epoxy resin having a butadiene structure having an aromatic structure), alicyclic epoxy resin (alicyclic epoxy resin having no aromatic structure or alicyclic epoxy resin having an aromatic structure), heterocyclic epoxy resin, spiro ring-containing epoxy resin (spiro ring-containing epoxy resin having no aromatic structure or spiro ring-containing epoxy resin having an aromatic structure), cyclohexanedimethanol type epoxy resin (cyclohexanedimethanol type epoxy resin having no aromatic structure or cyclohexanedimethanol type epoxy resin having an aromatic structure), naphthylene ether type epoxy resin, trimethylol type epoxy resin (trimethylol type epoxy resin having no aromatic structure or trimethylol type epoxy resin having an aromatic structure), tetraphenylmethane type epoxy resin, aminophenol type epoxy resin, and aromatic or aliphatic epoxy resins such as silicone-modified epoxy resin, etc.

[0028] Among these, the epoxy resin (A) more preferably contains at least one selected from the group consisting of bisphenol F type epoxy resins, bisphenol A type epoxy resins such as bisphenol A type epoxy resins, aminophenol type epoxy resins, naphthalene type epoxy resins, and alicyclic epoxy resins, and more preferably contains an aminophenol type epoxy resin. In particular, by containing an aminophenol type epoxy resin, perhaps due to the improved solubility of dicyandiamide (C), even when the content of dicyandiamide (C) is small (that is, 0.1% by mass or less), the creep suppression effect by including it tends to be improved.

[0029] Specific examples of the liquid epoxy resin include "YDF-8170" (bisphenol F type epoxy resin), "YDF-8125" (bisphenol A type epoxy resin), "ZX-1658", "ZX-1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical & Material Co., Ltd., "HP-4032", "HP-4032D", "HP-4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "jER828US", "jER828EL" (bisphenol A type epoxy resin), "jER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD", "EP3980S" (aminophenol type epoxy resin), "YX7400" (high resilience epoxy resin) manufactured by Mitsubishi Chemical Corporation, "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, and "Celloxide 2021P" (alicyclic epoxy resin) manufactured by Daicel Corporation.

[0030] Specific examples of the solid epoxy resin include "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol novolak-type epoxy resin), "N-695" (cresol novolak-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (dicyclopentadiene-type epoxy resin), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin), "NC-7000-L" (naphthol novolak-type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", "NC-3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol-type epoxy resin), "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "jER157S70" (bisphenol novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

[0031] The epoxy equivalent of the epoxy resin (A) is not particularly limited, but for example, it is preferably 30 to 1000 g / eq, more preferably 40 to 500 g / eq, and still more preferably 50 to 300 g / eq.

[0032] The content of the epoxy resin (A) with respect to the above epoxy resin composition (100% by mass) is not particularly limited, but for example, it is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 12% by mass or more, particularly preferably 15% by mass or more, and most preferably 18% by mass or more. Also, for example, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, particularly preferably 40% by mass or less, and most preferably 35% by mass or less. When the content of the epoxy resin (A) is within the above range, the thermal expansibility of the cured product is reduced, and the toughness tends to be improved.

[0033] · Aromatic amine compound (B) The aromatic amine compound (B) has the characteristic of initiating, proceeding, or accelerating the polymerization of the epoxy resin. Therefore, when the epoxy resin composition of the present invention is used as an underfill, the viscosity increases before the composition wets and spreads on the chip, and it becomes possible to suppress creeping. The aromatic amine compound (B) can be used alone or in combination of two or more.

[0034] The aromatic amine compound (B) may be liquid or solid at normal temperature (25°C), but is preferably liquid. When the aromatic amine compound (B) is liquid at 25°C, its viscosity is not particularly limited. For example, it is preferably 5000 mPa·s or less, more preferably 3000 mPa·s or less, still more preferably 2000 mPa·s or less, particularly preferably 1000 mPa·s or less, and most preferably 500 mPa·s or less. Also, for example, it is preferably 1 mPa·s or more, more preferably 10 mPa·s or more. When the viscosity of the aromatic amine compound (B) is within the above range, the solubility of dicyandiamide (C) is improved. Therefore, even when the content of dicyandiamide (C) is small (i.e., 0.1% by mass or less), the creeping suppression effect by including dicyandiamide tends to be exhibited.

[0035] Among these, when the aromatic amine compound (B) contains an aromatic amine compound having a viscosity of 2000 mPa·s or less at 25°C (referred to as "low-viscosity aromatic amine compound"), the content of the low-viscosity aromatic amine compound in the aromatic amine compound (B) is not particularly limited. For example, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 60% by mass.

[0036] Examples of the aromatic amine compound (B) include 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone.

[0037] The equivalent weight (molecular weight per functional group) of the aromatic amine compound (B) is not particularly limited. For example, it is preferably 10 to 600 g / eq, more preferably 20 to 400 g / eq, and still more preferably 30 to 200 g / eq.

[0038] The content of the aromatic amine compound (B) relative to the epoxy resin composition (100% by mass) of the present invention is not particularly limited. For example, it is preferably 0.1 to 90% by mass, more preferably 0.5 to 60% by mass, still more preferably 1 to 40% by mass, and particularly preferably 2 to 30% by mass. When the content of the aromatic amine compound (B) is within the above range, the creep suppression effect tends to be improved. In addition, the thermal expansibility of the cured product is reduced, and the toughness tends to be improved.

[0039] · Dicyandiamide (C) Dicyandiamide (C) initiates, progresses, or accelerates the polymerization of the epoxy resin. Examples of commercially available dicyandiamide include "CG1400" of Evonik Industries AG.

[0040] The content of dicyandiamide (C) relative to the epoxy resin composition (100% by mass) of the present invention is not particularly limited as long as it is 0.001 to 0.1% by mass. For example, it is preferably 0.001 to 0.08% by mass, more preferably 0.001 to 0.06% by mass, and still more preferably 0.001 to 0.049% by mass. When the content of dicyandiamide (C) is within the above range, the creep suppression effect is improved, and the pot life also tends to be prolonged.

[0041] · Siloxane (D) The polyether-modified polydimethylsiloxane (D) is a compound in which some or all of the methyl groups of the dimethylsiloxane chain are replaced with polyether chains. Since the above dimethylsiloxane chain is hydrophobic and the above polyether chain is hydrophilic, siloxane (D) as a whole has surfactant-like properties. By blending siloxane (D) into the epoxy resin composition of the present invention, the surface tension can be adjusted, so that creep can be suppressed more effectively. Siloxane (D) can be used alone or in combination of two or more.

[0042] Although the siloxane (D) is not particularly limited, it is preferably a siloxane represented by the following formula (1), for example. [Chemical formula]

[0043] In the above formula (1), R1 is the same or different and is a methyl group or a polyether chain. R2 is the same or different and is a methyl group or a polyether chain. However, at least one of R1 and R2 is a polyether chain. n is an integer from 1 to 105.

[0044] The polyether chain contained in the siloxane represented by the above formula (1) is not particularly limited as long as there is at least one, but is preferably 1 to 5, more preferably 1 to 3. That is, among R1 and R2, the polyether chain is preferably 1 to 5, more preferably 1 to 3.

[0045] The siloxane (D) is more preferably a siloxane represented by the following formula (2) or (3). [Chemical formula] [Chemical formula]

[0046] In the above formulas (2) and (3), R1 and R2 are the same as in formula (1), the same or different, and are a methyl group or a polyether chain, and are preferably a methyl group. n1 is an integer from 1 to 100. n2 is an integer from 1 to 5. Note that n1 and n2 indicate the number of repeating units in the structure within the parentheses. P in the formula is a polyether chain, and the left end of the polyether chain is bonded to the Si atom of the dimethylsiloxane chain. m is from 1 to 30.

[0047] The content of the siloxane (D) relative to the epoxy resin composition (100% by mass) of the present invention is not particularly limited, but for example, it is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass, still more preferably 0.001 to 0.05% by mass, and particularly preferably 0.002 to 0.01% by mass. When the content of the siloxane (D) is within the above range, the creep suppression effect is improved and the pot life also tends to be prolonged.

[0048] · Inorganic filler (E) The inorganic filler (E) is not particularly limited, but preferably has the following characteristics: (1) having the property of suppressing the volume shrinkage (curing shrinkage) caused by the curing reaction of the epoxy resin composition; (2) having the property of suppressing the volume change (thermal shrinkage) of the cured product due to heating, that is, having the effect of lowering the linear expansion coefficient by addition; or (3) having both of these characteristics.

[0049] Examples of the inorganic filler (E) include silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, calcium sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and inorganic particles with their surfaces treated. Among these, silica is preferred from the viewpoint of being able to increase the filling amount. The inorganic filler (E) can be used alone or in combination of two or more.

[0050] The inorganic filler (E) is preferably surface-treated with a coupling agent having a functional group such as an epoxy group, a (meth)acryloyl group, or an amino group (particularly a phenylamino group) from the viewpoint of setting the viscosity of the epoxy resin composition within an appropriate range. Examples of the coupling agent include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. For the surface treatment of the inorganic filler (E), one type of the above coupling agent can be used alone, or two or more types can be used in combination.

[0051] The shape of the inorganic filler (E) is not particularly limited, and examples thereof include spherical (true spherical, substantially true spherical, etc.), polyhedral, rod-shaped (cylindrical, prismatic, etc.), flat plate-shaped, flaky, and irregular shapes. Among these, a spherical shape is preferable from the viewpoint of achieving a high filling amount.

[0052] The average particle diameter of the inorganic filler (E) is not particularly limited, but for example, 1 nm to 10 μm is preferable, more preferably 0.1 to 5 μm, and still more preferably 0.2 to 2 μm. When the average particle diameter of the inorganic filler (E) is within the above range, since the particle diameter is not too large, even in a narrow gap, the injectability of the epoxy resin composition is less likely to decrease, and the viscosity of the epoxy resin composition can be adjusted to a viscosity that is easy to dispense. Note that two or more types of fillers having different average particle diameters may be used in combination for the purpose of adjusting the viscosity of the epoxy resin composition. In this specification, the method for measuring the average particle diameter of the inorganic filler (E) is not particularly limited, but for example, it can be measured using a laser diffraction / scattering particle size distribution measuring device (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0053] The content of the inorganic filler (E) relative to the above epoxy resin composition (100% by mass) is not particularly limited. For example, it is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. Also, although not particularly limited, for example, it is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. When the content of the inorganic filler (E) is within the above range, the effect of suppressing curing shrinkage and thermal shrinkage tends to be improved. Also, the effect of suppressing creep is improved, and the pot life also tends to be prolonged.

[0054] ·Elastomer (F) The elastomer (F) can impart toughness to the cured product. Therefore, when the above epoxy resin composition containing the elastomer (F) is used as an underfill, the occurrence of cracks is reduced, and high product reliability is exhibited. The elastomer (F) is not particularly limited. For example, butadiene-based elastomers, silicone-based elastomers, acrylic copolymers, styrene-butadiene-based elastomers, butadiene-acrylonitrile-2,3-epoxypropyl methacrylate-divinylbenzene copolymers, butadiene-acrylonitrile-methacrylic acid-divinylbenzene copolymers, amino group-terminated butadiene-acrylonitrile copolymers, and carboxyl group-terminated butadiene-acrylonitrile copolymers are preferred. The elastomer (F) can be used alone or in combination of two or more.

[0055] The elastomer (F) is preferably a core-shell rubber particle. That is, it is preferably a core-shell rubber type elastomer. The core-shell rubber particle refers to a rubber particle composed of a core part and one or more shell layers covering the core part. By forming the core part of the core-shell rubber particle with a material having excellent flexibility and the shell layer with a material having excellent affinity for the components contained in the epoxy resin composition, particularly the epoxy resin (A), the core-shell rubber particle can exhibit good dispersibility in the epoxy resin composition and impart high toughness to its cured product. Also, the creep suppression effect tends to be improved.

[0056] In the above core-shell rubber particle, the core part is formed of a material having excellent flexibility. Examples of the material forming the core part include silicone rubber, butadiene rubber, styrene rubber, acrylic rubber, polyolefin rubber, and silicone / acrylic composite rubber. As the material forming the shell layer, a material having excellent affinity for the components (particularly the epoxy resin (A)) contained in the epoxy resin composition of the present invention is preferably used. Examples of the material forming the shell layer include bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy resins such as glycidyl methacrylate, and acrylic resins. The core-shell rubber particles can be used alone or in combination of two or more.

[0057] Examples of commercially available elastomers (F) include "Kaneka Ace MX-153", "Kaneka Ace MX-257", "Kaneka Ace MX-154", "Kaneka Ace MX-960", "Kaneka Ace MX-136", "Kaneka Ace MX-137", "Kaneka Ace MX-965", "Kaneka Ace MX-217", "Kaneka Ace MX-227M75", "Kaneka Ace MX-334M75", "Kaneka Ace MX-416", "Kaneka Ace MX-451" manufactured by Kaneka Corporation; "Metablen C-223A", "Metablen C-140A", "Metablen E-860A", "Metablen E-870A", "Metablen E-875A", "Metablen S-2100", "Metablen S-2200", "Metablen S-2260" manufactured by Mitsubishi Chemical Corporation; "Stafiloid IM-203", "Stafiloid IM-401", "Stafiloid IM-601", "Stafiloid AC3355", "Stafiloid AC3816" manufactured by Aika Industries Co., Ltd.; "Acryset BPA328", "Acryset BPF307" manufactured by Nippon Shokubai Co., Ltd.; "EP 2240 A", "EP 5340", "PU 5640", "VE3340", "XP1 / 0767" manufactured by Evonik Corporation, etc.

[0058] The content of the elastomer (F) with respect to the above epoxy resin composition (100% by mass) is not particularly limited. For example, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more. Also, the content is not particularly limited, but for example, it is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, still more preferably 7.5% by mass or less, particularly preferably 5.0% by mass or less, and most preferably 3.0% by mass or less.

[0059] · Coupling agent (G) The coupling agent (G) is not particularly limited. For example, silane coupling agents such as vinyl-based, glycidoxy-based, methacrylic-based, amino-based, mercapto-based, or imidazole-based; titanium coupling agents such as alkoxide-based, chelate-based, or acylate-based; and various coupling agents such as long-chain spacer type coupling agents like glycidoxy octyltrimethoxysilane or methacrylo octyltrimethoxysilane can be mentioned. The coupling agent (G) can be used alone or in combination of two or more kinds.

[0060] Examples of the above silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc.

[0061] The content of the coupling agent (G) with respect to the above epoxy resin composition (100% by mass) is not particularly limited. For example, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more. Also, the content is not particularly limited, but for example, it is preferably 5.0% by mass or less, more preferably 3.0% by mass or less. When the content of the coupling agent (G) is within the above range, the creep suppression effect tends to be improved.

[0062] · Pigment (H) The pigment (H) is not particularly limited. For example, carbon black, titanium black such as titanium nitride, black organic pigments, mixed-color organic pigments, and inorganic pigments can be used. Examples of the black organic pigment include perylene black and aniline black; examples of the mixed-color organic pigment include those pseudo-blackened by mixing at least two or more pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc.; examples of the inorganic pigment include graphite and metal fine particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, etc., metal oxides, composite oxides, metal sulfides, metal nitrides, etc. Among these, carbon black or titanium black is preferred. The pigment (H) can be used alone or in combination of two or more.

[0063] The content of the pigment (H) relative to the above epoxy resin composition (100% by mass) is not particularly limited. For example, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more. Also, the content is not particularly limited. For example, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0064] · Dispersant (I) When the dispersant (I) is used in combination with dicyandiamide (C), the creeping suppression effect tends to be improved. The dispersant (I) is not particularly limited, but a resin-type dispersant having an acidic group or a basic group is preferred. Examples of the above acidic group include a carboxyl group, a sulfo group, a phosphoric acid group, etc. Examples of the above basic group include a primary to tertiary amino group, a quaternary ammonium base, etc.

[0065] Resin-type dispersants having acidic groups include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyamino amidates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with a polyester having free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based ones, and the like. Resin-type dispersants having basic groups include, for example, nitrogen atom-containing graft copolymers, functional groups containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain, for resin types such as acrylic resins, polyester resins, and urethane resins, nitrogen atom-containing acrylic block copolymers or urethane-based polymer dispersants, and the like. Among these, the dispersant (I) is preferably a resin-type dispersant having a basic group such as a primary to tertiary amino group, because the creeping suppression effect is more remarkable.

[0066] Examples of commercially available dispersants (I) include "JONCRYL67", "JONCRYL678", "JONCRYL586", "JONCRYL611", "JONCRYL683", "JONCRYL690", "JONCRYL57J", "JONCRYL60J", "JONCRYL61J", "JONCRYL62J", "JONCRYL63J", "JONCRYLHPD-96J", "JONCRYL501J", "JONCRYLPDX-6102B" manufactured by BASF Japan Ltd.; "DISPERBYK109", "DISPERBYK180", "DISPERBYK185", "DISPERBYK187", "DISPERBYK190", "DISPERBYK191", "DISPERBYK192", "DISPERBYK194", "DISPERBYK2010", "DISPERBYK2015", "DISPERBYK2090", "DISPERBYK2091", "DISPERBYK2095", "DISPERBYK2155" manufactured by BYK-Chemie Japan Co., Ltd.; "SOLSPERSE24000", "SOLSPERSE32000", "SOLSPERSE39000", "SOLSPERSE41000" manufactured by Lubrizol Japan Ltd.; "SMA1000H", "SMA1440H", "SMA2000H", "SMA3000H", "SMA17352H" manufactured by Sartomer Co., Ltd. Among these, "DISPERBYK180", "DISPERBYK185", "DISPERBYK109", "DISPERBYK192", "DISPERBYK191", etc., which are solvent-free dispersants, are preferred.

[0067] The amine value of the dispersant (I) is not particularly limited, but for example, it is preferably 5 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, still more preferably 20 to 120 mgKOH / g, particularly preferably 30 to 100 mgKOH / g, and most preferably 40 to 80 mgKOH / g.

[0068] The content of the dispersant (I) relative to the above epoxy resin composition (100% by mass) is not particularly limited. For example, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more. Also, although its content is not particularly limited, for example, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0069] · Curing agent (J) The curing agent (J) is not particularly limited as long as it can initiate, progress, or accelerate the polymerization of the epoxy resin. Examples include acid anhydride-based curing agents, phenol-based curing agents, and imidazole-based curing agents. In the present invention, the aromatic amine compound (B) is not included in the curing agent (J). The curing agent (J) can be used alone or in combination of two or more.

[0070] Examples of the above acid anhydride-based curing agents include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methyl nadic anhydride. Examples of the above phenol-based curing agents include phenol novolak resin, cresol novolak resin, naphthol-modified phenol resin, dicyclopentadiene-modified phenol resin, and p-xylene-modified phenol resin. Examples of the above imidazole-based curing agents include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Also, as the imidazole-based curing agent, microcapsule-type imidazole-based curing agents are also included.

[0071] · Curing accelerator (K) The curing accelerator (K) has the property of accelerating the curing of the epoxy resin. The curing accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Commercially available products include 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product name "2P4MZ"), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (manufactured by Shikoku Kasei Co., Ltd., product name "2MZA"), dicyandiamide, and the like. Further, encapsulated imidazoles called microcapsule-type imidazoles or epoxy adduct-type imidazoles may be used. For example, "HX3941HP", "HXA3942HP", "HXA3922HP", "HXA3792", "HX3748", "HX3721", "HX3722", "HX3088", "HX3741", "HX3742", "HX3613" (all manufactured by Asahi Kasei Chemicals Corporation), "PN-23J", "PN-40J", "PN-50" (manufactured by Ajinomoto Fine-Techno Co., Inc.), FXR-1121 (manufactured by Fuji Kasei Kogyo Co., Ltd.), and the like. The curing accelerator (K) can be used alone or in combination of two or more.

[0072] Since the curing accelerator (K) has the property of accelerating the curing of the epoxy resin, when the epoxy resin composition contains the curing accelerator (K), the curing reaction can be completed before creeping occurs. Therefore, from the viewpoint of suppressing creeping, it is preferable that the epoxy resin composition of the present invention contains the curing accelerator (K).

[0073] · Other components (L) The above epoxy resin composition may contain components other than the epoxy resin (A), aromatic amine compound (B), dicyandiamide (C), siloxane (D), inorganic filler (E), elastomer (F), coupling agent (G), pigment (H), dispersant (I), curing agent (J), and curing accelerator (K) (hereinafter referred to as "other components (L)"). Examples of the other components (L) include curable compounds other than the epoxy resin (A), thermoplastic resins such as polyethylene resin, polyester resin, polyurethane resin, and polyamide resin, surfactants other than the siloxane (D), ion trap agents, leveling agents, antioxidants, defoaming agents, flame retardants, reactive diluents, solvents, and the like. The other components (L) can be used alone or in combination of two or more kinds.

[0074] The content of the other components (L) with respect to the above epoxy resin composition (100% by mass) is not particularly limited as long as the effects of the present invention are not impaired. For example, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less. Also, although not particularly limited, for example, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.

[0075] (Physical properties and manufacturing method of epoxy resin composition) The creeping length (μm) of the above epoxy resin composition is not particularly limited. For example, it is preferably less than 660 μm, more preferably 650 μm or less, still more preferably 600 μm or less, particularly preferably 550 μm or less, and most preferably 500 μm or less. The creeping length (μm) can be determined by the method described in the examples below.

[0076] The viscosity (Pa·s, initial viscosity) of the above epoxy resin composition at 25°C is not particularly limited. For example, 0.1 to 300 Pa·s is preferable, more preferably 0.3 to 150 Pa·s, still more preferably 0.5 to 80 Pa·s, particularly preferably 0.8 to 50 Pa·s, and most preferably 1 to 30 Pa·s. When the viscosity is within the above range, filling into the gap tends to be easy. The above viscosity can be measured as the viscosity when rotated at 50 rpm for 1 minute at a liquid temperature of 25°C using a Brookfield viscometer (model number: HBDV-1, manufactured by Brookfield Engineering Laboratories, Inc.) as described in the examples below.

[0077] The viscosity (Pa·s, viscosity of the sample after holding for 24 hours) of the above epoxy resin composition after holding at 25°C for 24 hours is not particularly limited. For example, 0.1 to 500 Pa·s is preferable, more preferably 0.3 to 300 Pa·s, still more preferably 0.5 to 100 Pa·s, particularly preferably 0.8 to 80 Pa·s, and most preferably 1 to 60 Pa·s. When the viscosity is within the above range, filling into the gap tends to be easy. The measuring method of the above viscosity is as described above.

[0078] The thickening ratio at 25°C calculated by the following formula for the above epoxy resin composition is not particularly limited. For example, less than 1.8 is preferable, more preferably 1.75 or less, still more preferably 1.7 or less, particularly preferably 1.6 or less, and most preferably 1.5 or less. Thickening ratio = Viscosity of the sample after holding for 24 hours (Pa·s) / Initial viscosity (Pa·s)

[0079] The above epoxy resin composition can be prepared by a known and commonly used method. For example, an epoxy resin (A), an aromatic amine compound (B), dicyandiamide (C), and at least one selected from the group consisting of, if necessary, a siloxane (D), an inorganic filler (E), an elastomer (F), a coupling agent (G), a pigment (H), a dispersant (I), a curing agent (J), a curing accelerator (K), and other components (L) are introduced into a suitable mixer simultaneously or separately, and heated if necessary to be melted while stirring and mixing to obtain the above epoxy resin composition. When the epoxy resin (A) is solid, it is preferably liquefied or fluidized by heating for mixing. When it is difficult to uniformly disperse the inorganic filler (E) in the epoxy resin composition, the epoxy resin (A) and the inorganic filler (E) are heated and mixed to uniformly disperse the inorganic filler (E) in the epoxy resin (A), and then cooled if necessary, and further components such as the aromatic amine compound (B) are mixed to prepare the above epoxy resin composition.

[0080] The above mixer is not particularly limited, and examples include a roll mill, a Lycra machine, a Henschel mixer, a tumbler, a self-revolving and planetary mill, a planetary mixer, etc. equipped with a stirring device and a heating device. The mixing ratio of each component is appropriately set according to the content ratio of each component in the epoxy resin composition.

[0081] The above epoxy resin composition can be preferably used as a material (epoxy resin composition for semiconductor encapsulation) for encapsulating materials such as semiconductor elements, wirings, and solders (solder bumps) disposed on a substrate in a semiconductor device. By using the above epoxy resin composition as an epoxy resin composition for semiconductor encapsulation, a highly reliable encapsulant can be manufactured. Further, the above epoxy resin composition can be preferably used as a material (epoxy resin composition for flip-chip type semiconductor encapsulation) for encapsulating semiconductor elements and the like disposed on a substrate in a flip-chip type semiconductor device. Specifically described, by filling the above epoxy resin composition in the gap between a semiconductor element or the like and the substrate and performing thermosetting, while encapsulating the bump electrodes present in the above gap, the semiconductor element and the substrate are fixed to each other as an encapsulant, thereby improving the thermal cycle resistance.

[0082] The above epoxy resin composition for semiconductor encapsulation is used, for example, as an underfill such as capillary underfill, liquid mold underfill, secondary underfill, and pre-supplied type underfill, a grab top material, and a liquid compression molding material. The above epoxy resin composition is not limited to the use as the above epoxy resin composition for semiconductor encapsulation, and can be used, for example, as an adhesive for fixing, joining, or protecting components constituting electronic components.

[0083] The above epoxy resin composition for semiconductor encapsulation is particularly used for the purpose of encapsulating a substrate and a semiconductor element disposed on the substrate, and it is preferable that the semiconductor element is used for an application characterized in that the back side surface with respect to the orientation surface with the substrate is subjected to backside metallization treatment.

[0084] (Cured product of epoxy resin composition) A cured product is formed by curing the above epoxy resin composition. The curing method is not particularly limited. For example, it is carried out by subjecting the epoxy resin composition to a heat treatment. The temperature of the heat treatment is not particularly limited. For example, 60 to 200 °C is preferable, and 80 to 180 °C is more preferable. The time of the heat treatment is not particularly limited. For example, 0.1 to 5 hours is preferable, and 0.5 to 3 hours is more preferable.

[0085] (Semiconductor device) The semiconductor device of the present invention includes a substrate, a semiconductor element disposed on the substrate, and a cured product of the epoxy resin composition that seals the semiconductor element. The semiconductor device is preferably a flip chip type semiconductor device. The flip chip type semiconductor device has a structure in which an electrode portion on the substrate and a semiconductor element are connected via bump electrodes. Further, in the semiconductor device, the gap between the semiconductor element and the substrate is sealed by the cured product (sealing body) of the epoxy resin composition.

[0086] The semiconductor device particularly includes a substrate and a semiconductor element disposed on the substrate, and it is preferable that the back surface of the semiconductor element with respect to the orientation surface with the substrate is subjected to backside metallization treatment.

[0087] A semiconductor device can be manufactured by filling the gap between the substrate and the semiconductor element disposed on the substrate with the epoxy resin composition (filling step) and heating and curing the epoxy resin composition (sealing step). The method for filling the gap with the epoxy resin composition is not particularly limited. For example, while heating the substrate to 50 to 120 °C, the epoxy resin composition is applied to one end of the substrate or the semiconductor element, and the gap between the substrate and the semiconductor element is filled with the epoxy resin composition by capillary action. After filling the gap with the epoxy resin composition, the substrate is heated at a predetermined temperature for a predetermined time, specifically, at the temperature and time described in the heat treatment for forming the above cured product, and the gap is sealed.

Examples

[0088] The present invention will be described in more detail below based on examples, but the present invention is not limited to the examples.

[0089] Epoxy resin (A), aromatic amine compound (B), dicyandiamide (C), inorganic filler (E), coupling agent (G), and pigment (H), and, if necessary, 1 or more selected from the group consisting of siloxane (D), elastomer (F), and dispersant (I) were appropriately selected and mixed so as to have the blending ratios shown in Table 1, thereby preparing the epoxy resin compositions of Examples 1 to 17, Comparative Examples 1 and 2. The numerical values regarding each composition in Table 1 indicate parts by mass.

[0090] Each component in Table 1 will be described below. · Epoxy resin (A) YDF-8170 (product name): Bisphenol F type epoxy resin, epoxy equivalent 160 g / eq, viscosity at 25 °C is 1000 - 1500 mPa·s (liquid), manufactured by Nippon Steel Chemical & Material Co., Ltd. jER630 (product name): Aminophenol type epoxy resin, epoxy equivalent 98 g / eq, viscosity at 25 °C is 700 mPa·s (liquid), manufactured by Mitsubishi Chemical Corporation HP-4032D (product name): Naphthalene type epoxy resin, epoxy equivalent 142 g / eq, viscosity at 50 °C is 520 mPa·s (liquid), manufactured by DIC Corporation ZX-1658GS (product name): Cycloaliphatic diglycidyl ether, epoxy equivalent 133 g / eq, viscosity at 25 °C is 50 mPa·s or less (liquid), manufactured by Nippon Steel Chemical & Material Co., Ltd. · Aromatic amine compound (B) HD A-A / product name is "KAYAHARD A-A": 4,4'-diamino-3,3'-diethyldiphenylmethane, amine equivalent 64 g / eq, viscosity at 25 °C is 2500 mPa·s (liquid), manufactured by Nippon Kayaku Co., Ltd. Etcure 100 Plus (product name): Diethyltoluenediamine, amine equivalent 45 g / eq, viscosity at 25 °C is 160 mPa·s (liquid), manufactured by Albemarle Corporation · Dicyandiamide (C) CG1400 (Product Name): Dicyandiamide, manufactured by Evonik Industries AG · Siloxane (D) KF-6013 (Product Name): Polyether-modified organopolysiloxane, silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd. · Inorganic filler (E) SE2200-SEE (Product Name): Silicon dioxide with an average particle size of 1.5 μm and surface treated with 3-glycidoxypropyltrimethoxysilane, manufactured by Admatechs Co., Ltd. SE1050-SEO (Product Name): Silicon dioxide with an average particle size of 0.3 μm and surface treated with 3-glycidoxypropyltrimethoxysilane, manufactured by Admatechs Co., Ltd. YA010A-JGP (Product Name): Silicon dioxide with an average particle size of 10 nm and surface treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (bisphenol F type epoxy resin: mass ratio of silicon dioxide is 7:3), manufactured by Admatechs Co., Ltd. The values in Table 1 are the mass of the elastomer, and the mass fraction of the bisphenol F type epoxy resin is added to YDF-8170 · Elastomer (F) MX965: Product Name / Kaneka MX965, manufactured by Kaneka Corporation, bisphenol F type epoxy resin containing core-shell type silicone elastomer (bisphenol F type epoxy resin: mass ratio of core-shell type silicone elastomer is 75:25), epoxy equivalent is 224. The values in Table 1 are the mass of the elastomer, and the mass fraction of the bisphenol F type epoxy resin is added to YDF-8170 · Coupling agent (G) KBM-403 (Product Name): 3-Glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. · Pigment (H) Black 4: Product Name / Special Black 4, carbon black, manufactured by Orion Engineered Carbons S.A. · Dispersant (K) BYK180: Product Name / DISPERBYK180, polymer wetting dispersant, amine value 94 mgKOH / g, manufactured by BYK-Chemie GmbH

[0091] (Evaluation 1: Creeping Evaluation) A test piece was prepared by fixing a Si chip (semiconductor element) on a substrate (FR4) and subjected to plasma treatment. While heating this test piece on a hot plate at 110 °C, the epoxy resin compositions of Examples 1 to 17, Comparative Examples 1 and 2 were applied to the end face of the Si chip to form a fillet, and then cured at 165 °C for 120 minutes by a forced-air constant-temperature oven (manufactured by Yamato Scientific Co., Ltd.). After that, the length of creeping was measured with a microscope. The results are described in "Creeping Length (μm)" in Table 1.

[0092] (Evaluation 2: Measurement of Viscosity at 25 °C) Regarding the viscosity (Pa·s) at 25 °C immediately after the preparation of the epoxy resin compositions of Examples 1 to 17, Comparative Examples 1 and 2, a Brookfield viscometer (model number: RVDV-1, manufactured by Brookfield, using spindle SC4-14) was used to measure the viscosity (initial viscosity) when rotated at 50 rpm for 1 minute at a liquid temperature of 25 °C. The results are described in "Viscosity (Pa·s)" in Table 1.

[0093] The above epoxy resin composition was placed in a sealed container and held at 25 °C for 24 hours. The viscosity of the obtained sample was measured in the same procedure as above, and the thickening ratio, which is an index of the pot life, was determined by the following formula. The results are described in "Thickening Ratio" in Table 1. Thickening ratio = Viscosity of the sample after holding for 24 hours (Pa·s) / Initial viscosity (Pa·s)

[0094]

Table 1

Claims

1. An epoxy resin composition comprising an epoxy resin (A), an aromatic amine compound (B), and dicyandiamide (C), wherein the content of dicyandiamide (C) is 0.001 to 0.1% by mass.

2. The epoxy resin composition according to claim 1, further comprising a polyether-modified polydimethylsiloxane (D).

3. The epoxy resin composition according to claim 2, wherein the content of the polyether-modified polydimethylsiloxane (D) is 0.0001 to 0.1% by mass.

4. The epoxy resin composition according to claim 1 or 2, wherein the content of dicyandiamide (C) is 0.001 to 0.049% by mass.

5. The epoxy resin composition according to claim 1 or 2, wherein the viscosity of the epoxy resin (A) and / or the aromatic amine compound (B) is 2000 mPa·s or less.

6. The epoxy resin composition according to claim 1 or 2, further comprising an inorganic filler (E), wherein the content of the inorganic filler (E) is 40 to 80% by mass.

7. The epoxy resin composition according to claim 1 or 2, further comprising an elastomer (F).

8. The epoxy resin composition according to claim 1 or 2, further comprising a coupling agent (K).

9. The epoxy resin composition according to claim 1 or 2, further comprising a pigment (H).

10. The epoxy resin composition according to claim 1 or 2, which is used for semiconductor encapsulation.

11. The epoxy resin composition according to claim 10, which is an underfill.

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

13. A semiconductor device comprising a substrate, a semiconductor element disposed on the substrate, and the cured product according to claim 12 for encapsulating the semiconductor element.

14. A method for manufacturing a semiconductor device, comprising a step of filling a gap between a substrate and a semiconductor element disposed on the substrate with the epoxy resin composition according to claim 1 or 2, and a step of heating and curing the epoxy resin composition. ​

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