Epoxy resin composition

Abstract

Provided is an epoxy resin composition which has excellent temporary adhesiveness and can inhibit the substrate from warping during final hardening.　The epoxy resin composition comprises an epoxy resin (A), a hardener (B), a latent hardening catalyst (C), and an inorganic filler (D), wherein the molar ratio of reactive groups contained in the hardener (B) to epoxy groups contained in the epoxy resin (A) is 0.35-0.85 and the proportions of the latent hardening catalyst (C) and the inorganic filler (D) are 10-16 mass% and 35-67 mass%, respectively, with respect to the resin component (100 mass%) of the composition.

Description

Epoxy resin composition 【0001】 The present invention relates to an epoxy resin composition. 【0002】 Semiconductor packages are used for the purpose of protecting semiconductor chips from external shocks and environmental factors (humidity and dust), and for ensuring the stable operation of semiconductors. These packages are generally composed of a protective member called a LID and a stiffener which is a supporting member for supporting the substrate and the chip. 【0003】 The LID plays an important role in protecting the entire package against environmental factors and ensuring high reliability of the chip. The LID is generally made of a metal material such as aluminum or copper, and has the role of improving heat conductivity and efficiently dissipating (heat dissipation) the heat generated by the chip. The stiffener has the purpose of reinforcing so that the package and the substrate are not deformed by physical stress (bending or twisting), and plays an important role in maintaining the stability and reliability of the product especially during the progress of high-density mounting. In a semiconductor package, when adhering the LID and the stiffener to the substrate, it is common to use an adhesive containing a curable resin. 【0004】 As a method of using the adhesive, on a substrate on which a semiconductor chip is mounted, after applying the adhesive to the outer edge portion thereof, the LID and the stiffener are mounted on the substrate through the adhesive, and after temporary adhesion by heat and pressure, the semiconductor package is obtained by full curing. Therefore, the adhesive used for adhering members such as the LID and the stiffener to the substrate is required to have high adhesive strength and reliability. 【0005】 Japanese Patent Application Laid-Open No. 2006-222406 【0006】 In recent years, from the viewpoint of improving productivity, shortening of the temporary adhesion time has been required. That is, the adhesive is required to have a property (referred to as "temporary adhesiveness" in this specification) of exhibiting sufficient adhesive strength even when the heating time is short. When the temporary adhesiveness is low, there arises a problem that peeling between the substrate and the member occurs during the subsequent process or full curing. 【0007】Furthermore, substrates on which semiconductor chips are mounted may warp due to the effects of the encapsulating material (Figure 4(a)). Using an adhesive that applies a stress to the substrate that counteracts the warping caused by the encapsulating material can reduce the warping of the substrate (Figure 4(c)). Therefore, when bonding components such as LIDs and stiffeners to a substrate, adhesives with the above-mentioned properties are required. 【0008】 Therefore, the object of the present invention is to provide an epoxy resin composition that exhibits excellent temporary adhesion and can suppress warping of the substrate during the final curing process. 【0009】 The inventors of this invention, after diligent research to achieve the above objectives, discovered that the above problems can be solved by incorporating specific components into an epoxy resin composition. This invention was completed based on these findings. 【0010】 In other words, the present invention provides an epoxy resin composition comprising an epoxy resin (A), a curing agent (B), a latent curing catalyst (C), and an inorganic filler (D), wherein the molar ratio of reactive groups contained in the curing agent (B) to epoxy groups contained in the epoxy resin (A) is 0.35 to 0.85, the content of the latent curing catalyst (C) relative to the resin component (100% by mass) in the composition is 10 to 16% by mass, and the content of the inorganic filler (D) is 35 to 67% by mass. 【0011】 The epoxy resin composition described above preferably contains an amine-epoxy adduct type latent curing catalyst (C) as the latent curing catalyst. 【0012】 The epoxy resin composition described above preferably contains a phenolic curing agent as the curing agent (B). 【0013】 The epoxy resin composition described above preferably contains at least one epoxy resin (A) selected from the group consisting of bisphenol-type epoxy resins, cyclohexane-type epoxy resins, and aliphatic epoxy resins. 【0014】 The epoxy resin composition described above preferably further contains a silane coupling agent (E). 【0015】 The epoxy resin composition described above is preferably an adhesive for LID or stiffener. 【0016】 The epoxy resin composition of the present invention exhibits excellent temporary adhesion and can suppress substrate warping during full curing. Therefore, semiconductor packages obtained by using the above epoxy resin composition as an adhesive can be manufactured with high reliability and high productivity. 【0017】 This is a top view of a semiconductor chip-mounted substrate. This is a side view of a semiconductor chip-mounted substrate in the semiconductor package manufacturing method of the present invention. This is a side view of a semiconductor chip-mounted substrate in the semiconductor package manufacturing method of the present invention. This is a model in which warping of a semiconductor chip-mounted substrate is reduced by using the epoxy resin composition of the present invention. (a) is a semiconductor chip-mounted substrate in which warping has occurred due to the effect of the encapsulant. (b) shows the process of mounting a component (LID) on the semiconductor chip-mounted substrate of (a) and bonding the component and the substrate using the epoxy resin composition of the present invention. (c) is a diagram in which the warping of the substrate is reduced (corrected) by curing the epoxy resin composition of the present invention. 【0018】 <Epoxy Resin Composition> The epoxy resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), a latent curing catalyst (C), and an inorganic filler (D), wherein the molar ratio of reactive groups contained in the curing agent (B) to epoxy groups contained in the epoxy resin (A) is 0.35 to 0.85, the content of the latent curing catalyst (C) relative to the resin component (100% by mass) in the composition is 10 to 16% by mass, and the content of the inorganic filler (D) relative to the epoxy resin composition (100% by mass) is 35 to 67% by mass. 【0019】The molar ratio of reactive groups in the curing agent (B) to epoxy groups in the epoxy resin (A) can be calculated by dividing the total molar amount of reactive groups in the component included as curing agent (B) in the epoxy resin composition by the total molar amount of epoxy groups in the component included as epoxy resin (A) in the epoxy resin composition. Here, if the curing agent (B) is, for example, an acid anhydride-based curing agent, the reactive group is a carboxyl group, and if it is a phenol-based curing agent, the reactive group is a phenolic hydroxyl group. When the above ratio is within the above range, the epoxy resin composition tends to exhibit better preliminary adhesion and the warping of the substrate during full curing tends to be reduced. In addition, the adhesive strength after full curing tends to be good. 【0020】 In the epoxy resin composition described above, the content of the latent curing catalyst (C) relative to the resin component (100% by mass) in the composition is 10 to 16% by mass. The resin component is, for example, epoxy resin (A) and curing agent (B). 【0021】 Epoxy resin (A) The epoxy resin composition, by containing epoxy resin (A), can impart high electrical insulation and excellent adhesion to its cured product. The number of epoxy groups in epoxy resin (A) is not particularly limited as long as it is one or more, but it is preferable that it be two or more (i.e., a polyfunctional type epoxy resin). Epoxy resin (A) can be used alone or in combination of two or more types. 【0022】 The epoxy resin (A) may be liquid or solid at room temperature (25°C), but from the viewpoint of the viscosity of the epoxy resin composition, it is preferable that it be liquid. Even if it is a solid epoxy resin, it can preferably be used if it becomes liquid as a mixture when used in combination with a liquid epoxy resin. 【0023】The epoxy resin (A) is not particularly limited, but examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bixylenol type epoxy resin, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, oxazoli Examples include dong ring-containing epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, fluorene-type epoxy resins, biphenyl aralkyl epoxy resins, aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylmethane-type epoxy resins, aminophenol-type epoxy resins, and silicone-modified epoxy resins. 【0024】 From the viewpoint of temporary adhesion, the epoxy resin composition described above preferably contains at least one selected from the group consisting of bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins, cyclohexane-type epoxy resins, and aliphatic epoxy resins as the epoxy resin (A). 【0025】 The epoxy equivalent of epoxy resin (A) is not particularly limited, but is preferably 30 g / eq or more, more preferably 60 g / eq or more, even more preferably 80 g / eq or more, and especially preferably 100 g / eq or more. Alternatively, it is preferably 1000 g / eq or less, more preferably 800 g / eq or less, even more preferably 600 g / eq or less, and especially preferably 500 g / eq or less. 【0026】Specific examples of liquid epoxy resins include "YDF-8170" and "YDF870GS" (both bisphenol F type epoxy resins), "YDF-8125" (bisphenol A type epoxy resin), "ZX-1658" and "ZX-1658GS" (both 1,4-cyclohexanedimethanol diglycidyl ether) from Nippon Steel Chemical & Material Co., Ltd.; "HP-4032," "HP-4032D," and "HP-4032SS" (all naphthalene type epoxy resins) from DIC Corporation; and "jER828US" and "jER828EL" (both bisphenol A type epoxy resins) from Mitsubishi Chemical Corporation. 806, jER807 (both bisphenol F type epoxy resins), jER152 (phenol novolac type epoxy resin), jER630, jER630LSD (both aminophenol type epoxy resins), YX7400N (aliphatic epoxy resin / diglycidyl ether of polytetramethylene glycol); ZX1059 (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; EX-721 (glycidyl ester type epoxy resin) and EX-171 (lauryl alcohol (EO)) manufactured by Nagase ChemteX Corporation. １５ Examples include glycidyl ether; "Adeka Resin EP-4005" and "Adeka Resin EP-4003S" (both bisphenol A type epoxy resins containing a polypropylene glycol structure) manufactured by ADEKA Corporation, "EP-3950L" (aminophenol type epoxy resin), and "EP3980S" (glycidylamine type epoxy resin); "AER9000" (PO-modified bisphenol type epoxy resin), "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins) manufactured by Asahi Kasei Corporation; "DER852" and "DER858" (both oxazolidone ring-containing epoxy resins) manufactured by Dow Chemical Ltd.; "FAE-2500" and "EPPN-501HY" (both trisphenolmethane type epoxy resins) manufactured by Nippon Kayaku Co., Ltd.; and "Celoxide 2021P" (alicyclic epoxy resin) manufactured by Daicel Corporation. 【0027】Specific examples of solid epoxy resins include "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both naphthalene-type tetrafunctional epoxy resins) from DIC Corporation, "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (all dicyclopentadiene-type epoxy resins), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", and "HP6000" (all naphthylene ether-type epoxy resins) from Nippon Kayaku Co., Ltd.; and "EPPN" from Nippon Kayaku Co., Ltd. -502H (trisphenolmethane type epoxy resin), "NC-7000-L" (naphthol novolac type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", "NC-3100" (all biphenyl type epoxy resins); "ESN475V" (naphthol type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H" and "YL6121" (both biphenyl type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), and "YX8800" (anthracene type epoxy resin); "OGSOL" manufactured by Osaka Gas Chemical Co., Ltd. Examples include "PG-100" and "OGSOL CG-500" (phenol novolac type epoxy resin); and "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), and "jER157S70" (bisphenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation. 【0028】The content of epoxy resin (A) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 4% by mass or more, more preferably 8% by mass or more, even more preferably 12% by mass or more, even more preferably 16% by mass or more, and particularly preferably 18% by mass or more. Also, is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less. When the content of epoxy resin (A) is within the above range, the epoxy resin composition exhibits better temporary adhesion and tends to reduce warping of the substrate during full curing. 【0029】 • Curing agent (B) The curing agent (B) is not particularly limited as long as it initiates, promotes, or accelerates the polymerization of the epoxy resin, but examples include acid anhydride-based curing agents and phenol-based curing agents. One type of curing agent (B) may be used alone, or two or more types may be used in combination. 【0030】 Examples of the above acid anhydride-based curing agents include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadoic anhydride. Examples of the above phenol-based curing agents include phenol novolac resins, cresol novolac resins, naphthol-modified phenol resins, dicyclopentadiene-modified phenol resins, and p-xylene-modified phenol resins. 【0031】 From the viewpoint of temporary adhesion and reduction of substrate warping during final curing, a phenolic curing agent (particularly a phenol novolac resin) is preferred for the curing agent (B). 【0032】The equivalent amount of the curing agent (B) is not particularly limited, but is preferably 30 g / eq or more, more preferably 60 g / eq or more, even more preferably 80 g / eq or more, and especially preferably 100 g / eq or more. Alternatively, it is preferably 600 g / eq or less, more preferably 400 g / eq or less, even more preferably 300 g / eq or less, and especially preferably 200 g / eq or less. 【0033】 The content of the curing agent (B) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 6% by mass or more. Alternatively, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 16% by mass or less. When the content of the curing agent (B) is within the above range, the epoxy resin composition exhibits better temporary adhesion and tends to reduce warping of the substrate during full curing. 【0034】 The content of the curing agent (B) relative to the epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Alternatively, it is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. When the content of the curing agent (B) is within the above range, the epoxy resin composition exhibits better temporary adhesion and tends to reduce warping of the substrate during full curing. 【0035】• Latent curing catalyst (C) The latent curing catalyst (C) does not have curing activity toward epoxy resin (A) at room temperature (25°C), but is activated by external stimuli such as heating or external pressure, and is a substance that promotes the curing of epoxy resin (A). The epoxy resin composition of the present invention, by containing the latent curing catalyst (C), exhibits excellent temporary adhesion and can suppress warping of the substrate during full curing. The latent curing catalyst (C) can be used alone or in combination of two or more types. 【0036】 Examples of latent curing catalysts (C) include imidazole compounds that are solid at room temperature; solid-disperse amine adduct-type latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems). 【0037】 Imidazole compounds that are solid at room temperature are not particularly limited, but examples include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)'). Examples include -ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl-(1)-ethyl)-azivoyldiamide, etc. 【0038】Regarding commercially available latent curing catalysts, amine-epoxy adduct type (amine adduct type) latent curing catalysts include "Amicure PN-23" (product name of Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), "Hardener X-3670S" (product name of ACR Co., Ltd.), Examples include "NovaCure HX-3742" (Asahi Kasei Corporation product name), "NovaCure HX-3721" (Asahi Kasei Corporation product name), "NovaCure HXA9322HP" (Asahi Kasei Corporation product name), "NovaCure HXA3922HP" (Asahi Kasei Corporation product name), "NovaCure HXA3932HP" (Asahi Kasei Corporation product name), "NovaCure HXA5945HP" (Asahi Kasei Corporation product name), "NovaCure HXA9382HP" (Asahi Kasei Corporation product name), and "FujiCure FXR1121" (T&K Toka Co., Ltd. product name). Furthermore, examples of urea-type adduct-based latent curing catalysts include "Fujicure FXE-1000" (product name of T&K TOKA Corporation) and "Fujicure FXR-1030" (product name of T&K TOKA Corporation). As the latent curing catalyst (C), a solid-disperse type amine adduct-based latent curing catalyst is preferred from the viewpoint of temporary adhesion. 【0039】 Some latent curing catalysts (C) are provided in the form of a dispersion in an epoxy resin (A). When using such a form of latent curing catalyst (C), the amount of dispersed epoxy resin is included in the amount of epoxy resin (A). 【0040】The content of the latent curing catalyst (C) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2% by mass or more, even more preferably 2.5% by mass or more, and particularly preferably 3% by mass or more. Alternatively, it is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less. When the content of the latent curing catalyst (C) is within the above range, the epoxy resin composition tends to exhibit better temporary adhesion. It also tends to exhibit good adhesive strength after full curing. 【0041】 The content of the latent curing catalyst (C) relative to the epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 4% by mass or more, more preferably 8% by mass or more, even more preferably 12% by mass or more, and particularly preferably 14% by mass or more. Alternatively, it is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. When the content of the latent curing catalyst (C) is within the above range, the epoxy resin composition tends to exhibit better temporary adhesion. Furthermore, it tends to exhibit good adhesive strength after full curing. 【0042】 - Inorganic filler (D) The inorganic filler (D) is not particularly limited, but it is preferable that it has the properties of (1) suppressing volume shrinkage (curing shrinkage) caused by the curing reaction of the epoxy resin composition, (2) suppressing volume change (thermal shrinkage) due to heating of the cured product, that is, having the effect of lowering the coefficient of linear expansion when added, or (3) having both of the above properties. 【0043】Examples of the inorganic filler (D) 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, gypsum, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and inorganic particles with their surfaces treated. Among these, silica is preferable from the viewpoint of being able to increase the filling amount. The inorganic filler (D) can be used alone or in combination of two or more kinds. 【0044】 From the viewpoint of making the viscosity of the epoxy resin composition within an appropriate range, the inorganic filler (D) is preferably one whose surface is treated with a coupling agent having a functional group such as an epoxy group, a (meth)acryloyl group, or an amino group (especially a phenylamino group). 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 (D), one kind of the above coupling agent can be used alone or two or more kinds can be used in combination. 【0045】 The shape of the inorganic filler (D) 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, spherical is preferable from the viewpoint of being able to achieve a high filling amount. 【0046】The average particle size of the inorganic filler (D) is not particularly limited. For example, it is preferably 1 nm to 10 μm, more preferably 3 nm to 8 μm, still more preferably 4 nm to 6 μm, and particularly preferably 6 nm to 3 μm. For the purpose of adjusting the viscosity of the epoxy resin composition, two or more inorganic fillers (D) having different average particle sizes may be used in combination. In this specification, the method for measuring the average particle size of the inorganic filler (D) is not particularly limited. 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.). 【0047】 The above epoxy resin composition preferably contains, as the inorganic filler (D), an inorganic filler (D1) having an average particle size of 80 nm to 10 μm and an inorganic filler (D2) having an average particle size of 1 nm or more and less than 80 nm. The average particle size of the inorganic filler (D1) is preferably 0.1 to 8 μm, more preferably 0.15 to 6 μm, still more preferably 0.2 to 4 μm, and particularly preferably 0.25 to 3 μm. The average particle size of the inorganic filler (D2) is preferably 2 to 60 nm, more preferably 3 to 40 nm, still more preferably 4 to 30 nm, and particularly preferably 6 to 20 nm. By including the inorganic filler (D1) and the inorganic filler (D2) as the inorganic filler (D) in the above epoxy resin composition, the adjustment of the liquid characteristics (e.g., viscosity) can be easily carried out. 【0048】 The content of the inorganic filler (D) with respect to the above epoxy resin composition (100% by mass) is not particularly limited as long as it is 35 to 67% by mass. For example, it is more preferably 37% by mass or more, still more preferably 39% by mass or more, and particularly preferably 40% by mass or more. When the content of the inorganic filler (D) is within the above range, the viscosity of the above epoxy resin composition is within an appropriate range, so that the workability is improved, and the warpage of the substrate during curing tends to be further reduced. 【0049】The content of inorganic filler (D) relative to epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass or more. Also, is preferably 400% by mass or less, more preferably 380% by mass or less, even more preferably 360% by mass or less, even more preferably 340% by mass or less, and particularly preferably 320% by mass or less. When the content of inorganic filler (D) is within the above range, the viscosity of the epoxy resin composition becomes within an appropriate range, improving workability and tending to further reduce warping of the substrate during curing. 【0050】 Silane coupling agent (E) The epoxy resin composition of the present invention may further contain a silane coupling agent (E). The silane coupling agent (E) is not particularly limited, but examples include vinyl-based, glycidoxy-based, methacrylic-based, amino-based, mercapto-based, or imidazole-based silane coupling agents. One type of silane coupling agent (E) may be used alone, or two or more types may be used in combination. 【0051】 Examples of the silane coupling agents mentioned above include 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. 【0052】 The content of the silane coupling agent (E) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. Also, is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less. 【0053】Other Components (F) The epoxy resin composition described above may contain components other than epoxy resin (A), curing agent (B), latent curing catalyst (C), inorganic filler (D), and silane coupling agent (E) (hereinafter referred to as "other components (F)"). Examples of other components (F) include curable compounds other than epoxy resin (A), thermoplastic resins such as polyethylene resin, polyester resin, polyurethane resin, and polyamide resin, curing accelerators, elastomers, surfactants, ion trapping agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants such as carbon black, reactive diluents, solvents, etc. Other components (F) can be used individually or in combination of two or more. 【0054】 The content of other components (F) relative to the epoxy resin composition (100% by mass) is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. Also, for example, it may be 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more. 【0055】 The solvent content relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less. 【0056】(Physical Properties and Manufacturing Method of Epoxy Resin Composition) The viscosity of the epoxy resin composition at 25°C is not particularly limited, but is preferably 1 to 200 Pa·s, more preferably 10 to 150 Pa·s, even more preferably 20 to 120 Pa·s, and particularly preferably 30 to 100 Pa·s. When the viscosity is within the above range, the gap-filling ability and workability of the epoxy resin composition are improved, and the warping of the wafer after molding tends to be reduced. The viscosity can be measured using a Brookfield viscometer (model: HB-DV1 No. 14 spindle, manufactured by Brookfield) at a liquid temperature of 25°C, when rotated at 50 rpm for 1 minute. 【0057】 The above epoxy resin composition can be prepared by known and conventional methods. For example, the epoxy resin composition can be obtained by introducing epoxy resin (A), curing agent (B), latent curing catalyst (C), inorganic filler (D), and optionally silane coupling agent (E) and other components (F) into a suitable mixer simultaneously or separately, and stirring and mixing them while melting them by heating as needed. If the epoxy resin (A) is solid, it is preferable to liquefy or fluidize it by heating before mixing. If it is difficult to uniformly disperse the inorganic filler (D) in the epoxy resin composition, the epoxy resin (A) and inorganic filler (D) may be heated and mixed to uniformly disperse the inorganic filler (D) in the epoxy resin (A), then cooled as needed, and further mixing in components such as the curing agent (B) to prepare the epoxy resin composition. 【0058】 The above-mentioned mixer is not particularly limited, but examples include a roll mill equipped with a stirring device and a heating device, a Leikai mill, a Henschel mixer, a tumbler, a self-rotating mill, a planetary mixer, etc. The mixing ratio of each component is appropriately set according to the content ratio of each component in the epoxy resin composition. 【0059】The epoxy resin composition described above can be preferably used as an adhesive for bonding protective members such as LIDs and support members such as stiffeners to a substrate (semiconductor chip mounting substrate) on which a semiconductor chip sealed with an encapsulant is mounted in a semiconductor package. In other words, the epoxy resin composition is an adhesive for protective members such as LIDs or support members such as stiffeners. By using the epoxy resin composition as an adhesive for the above application, a highly reliable semiconductor package can be obtained. 【0060】 <Semiconductor Package and Method for Manufacturing the Same> The semiconductor package of the present invention comprises a substrate, a semiconductor chip mounted on the substrate, and a sealing material for sealing the semiconductor chip, wherein the substrate and a member such as a protective member or a support member are bonded together via the epoxy resin composition. 【0061】 The present invention provides a method for manufacturing a semiconductor package, comprising: a step of preparing a semiconductor chip mounting substrate including a substrate, a semiconductor chip mounted on the substrate, and a sealing material for sealing the semiconductor chip (substrate preparation step); a step of applying the epoxy resin composition of the present invention to the semiconductor chip mounting substrate, and then attaching a component to the semiconductor chip mounting substrate via the epoxy resin composition to form a laminate (substrate bonding step); a step of temporarily bonding the component to the semiconductor chip mounting substrate (temporary bonding step); and a step of fully curing the laminate after temporary bonding (full curing step). 【0062】 The semiconductor package and its manufacturing method according to the present invention will be described below with reference to Figures 1 to 3. Figure 1 is a top view of a semiconductor chip mounted on a substrate 1. 2 is the epoxy resin composition of the present invention, 3 is the semiconductor chip, 4 is the encapsulant, and 5 is the substrate. Figures 2 and 3 are side views of the semiconductor chip mounted on a substrate 10 during the substrate bonding process, the temporary bonding process, and the final curing process. 11 is the semiconductor chip, 12 is the adhesive, 13 is the encapsulant, 14 is the component (LID), 15 is the epoxy resin composition of the present invention, and 16 is the substrate. 【0063】(Substrate preparation process) The substrate preparation process is a process of preparing a semiconductor chip mounted substrate 1 which includes a substrate 5, a semiconductor chip 3 mounted on the substrate 5, and a sealing material 4 for sealing the semiconductor chip 3. The material of the substrate 5 is not particularly limited, but examples include silicon wafers, silicon carbide wafers, sapphire wafers, compound semiconductor wafers (gallium phosphide, gallium arsenide, indium phosphide, gallium nitride), glass epoxy substrates, organic substrates (FR4 substrates), etc. 【0064】 (Substrate bonding process) The substrate bonding process involves applying the epoxy resin composition 15 of the present invention to the semiconductor chip mounting substrate 10, and then attaching the member 14 to the semiconductor chip mounting substrate 10 via the epoxy resin composition 15 to form a laminate. In this process, the area on the semiconductor chip mounting substrate 10 to which the epoxy resin composition 15 of the present invention is applied is not particularly limited, but it is preferably the outer edge of the substrate 16. 【0065】 (Temporary bonding process) The temporary bonding process is a process of temporarily bonding the member 14 to the semiconductor chip mounting substrate 10 of the laminate obtained through the substrate bonding process. The conditions for temporary bonding are not particularly limited, but the curing temperature is preferably 110 to 180°C, more preferably 120 to 160°C. The curing time is not particularly limited, but is preferably 5 to 300 seconds, more preferably 10 to 200 seconds, and even more preferably 20 to 100 seconds. During temporary bonding, heat treatment may be performed while applying pressure from the member 14 towards the substrate 16, or from the substrate 16 towards the member 14. 【0066】 (Main curing process) The main curing process is a process of fully curing the laminate that has been temporarily bonded after the temporary bonding process. The conditions for main curing are not particularly limited, but the curing temperature is preferably 110 to 180°C, more preferably 120 to 160°C. The curing time is not particularly limited, but is preferably 5 to 120 minutes, more preferably 10 to 80 minutes, and even more preferably 20 to 60 minutes. During main curing, heat treatment may be performed while applying pressure from the member 14 towards the substrate 16, or from the substrate 16 towards the member 14. 【0067】The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. 【0068】 The epoxy resin compositions of the examples and comparative examples were prepared by mixing each component to the proportions shown in Table 1. The values ​​for each component in Table 1 represent parts by mass. The "molar ratio of reactive groups in epoxy resin (A) and curing agent (B)" in the table is, strictly speaking, the "molar ratio of reactive groups contained in curing agent (B) to epoxy groups contained in epoxy resin (A)," and is the molar ratio calculated from the epoxy groups contained in the epoxy resin used in the examples or comparative examples and the phenolic hydroxyl groups in the phenolic curing agent used as curing agent (B). 【0069】The following describes each component in Table 1. • Epoxy resin (A) ZX-1658GS (product name): Cyclohexane-type epoxy resin (1,4-cyclohexanedimethanol diglycidyl ether), epoxy equivalent 132 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. YX7400N (product name): Aliphatic epoxy resin (bifunctional long-chain aliphatic glycidyl ether), epoxy equivalent 445 g / eq, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation YDF-8170 (product name): Bisphenol F-type epoxy resin, epoxy equivalent 159 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. • Curing agent (B) MEH-8005 (product name): Phenolic curing agent (allylated phenol novolac resin), curing agent equivalent (hydroxyl group equivalent) 135 g / eq, manufactured by Meiwa Chemical Industries, Ltd. • Latent curing catalyst (C) HXA9322HP: Product name / Novacure™ HXA9322HP, amine-epoxy adduct type, manufactured by Asahi Kasei Corporation (HXA9322HP is provided in the form of a dispersion (latent curing catalyst / mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin = 33 / 67 (mass ratio)) in which particulate latent curing catalyst is dispersed in epoxy resin (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (epoxy equivalent: 170)). The amount of latent curing catalyst (C) in Table 1 is indicated as the amount of latent curing catalyst.) ・Inorganic fillers (D) SE1050-SEO (product name): Silicon dioxide surface treated with 3-glycidoxypropyltrimethoxysilane, average particle size 0.3 μm, manufactured by Admatex Co., Ltd. SE5050-SEJ (product name): Silicon dioxide surface treated with 3-glycidoxypropyltrimethoxysilane, average particle size 1.5 μm, manufactured by Admatex Co., Ltd. TS720 (product name): Product name / Cabosil TS720, silicon dioxide surface treated with polydimethylsiloxane, average particle size 12 nm, manufactured by Cabot Co., Ltd. ・Silane coupling agent (E) KBM-403 (product name): 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. ・Other components (F) Black 4: Product name / Special Black 4 powder, carbon black, manufactured by Orion Engineered Carbon. 【0070】 The following explains each of the evaluations in Table 1. 【0071】 [Appearance of Cured Product] Two glass plates with a release agent applied to their surfaces were prepared. Spacers with a thickness of 350 μm were placed on the left and right ends of one glass plate. 2 to 3 g of the epoxy resin composition of the example and comparative example was applied to the center of the glass plate, and the adhesive was spread with the other glass plate, sandwiching the adhesive between the two glass plates. The two glass plates were fixed with clips and heated in a forced-air dryer at 150°C for 30 minutes to cure the composition and produce a cured product. The cured product was peeled off the glass, and its appearance was evaluated according to the following evaluation criteria. The results are shown in the "Appearance of Cured Product" section of Table 1. ・Evaluation Criteria ○: When viewed visually, the cured product is uniformly black overall. ×: When viewed visually, part or all of the cured product is gray. 【0072】[Adhesion Evaluation] A polyimide film (thickness 120 μm) with a 2 mm diameter hole for temporary adhesion was used to apply the epoxy resin compositions of the examples and comparative examples in a circular pattern onto a Ni plate (2 cm long x 2 cm wide x 1 mm thick). A 2 mm thick SiN chip was placed on the applied epoxy resin composition to prepare a test specimen. The obtained test specimen was heat-treated using a forced-air dryer at 150°C for 90 seconds. The die shear strength (N) of the test specimen after heat treatment was measured using a bond tester (DAGE-4000PLUS, manufactured by DAGE). The results are listed in Table 1 under "Die Shear Strength (N) during Short-Time Heating". 【0073】 In this evaluation, if the die shear strength is above a certain value (for example, 42 N or higher), the epoxy resin composition can be evaluated as having excellent temporary adhesion, as it possesses sufficient adhesive strength even in a short time. 【0074】 - Adhesion strength after post-curing A polyimide film (thickness 120 μm) with a 2 cm x 1 cm hole was used to apply the epoxy resin compositions of the examples and comparative examples to the short edge of a 5 cm x 3 cm glass epoxy substrate. A Ni plate (2 cm x 2 cm x 1 mm thick) was placed on the applied epoxy resin composition so that approximately half of its area was in contact with the glass epoxy substrate, and it was fixed with clips. The laminate of the fixed glass epoxy substrate and Ni plate was heat-treated in a forced-air dryer at 150°C for 90 seconds. After removing the laminate from the forced-air dryer, the clips were removed, and it was heat-treated again in the forced-air dryer at 150°C for 30 minutes to obtain a test specimen. The tensile strength (N) of the obtained test specimen was measured using a universal tester (Autograph AGS-X, manufactured by Shimadzu Corporation). After measurement, the bonding area of ​​the test specimen (the area of ​​the bonded portion between the glass epoxy substrate and the Ni plate) was measured using a digital microscope (VHX-2000, manufactured by Keyence Corporation), and the bond strength (MPa) after post-curing was calculated using the following formula. The results are listed in Table 1 under "Bond Strength (MPa) after Post-Cure". Bond Strength (MPa) after Post-Cure = Tensile Strength (N) / Bonding Area (mm²) ２ ) 【0075】In this evaluation, if the adhesive strength is above a certain value (for example, 4.8 MPa or higher), the epoxy resin composition can be evaluated as having sufficient adhesive strength at the time of curing. 【0076】 [Warpage Amount] - Warpage amount on glass plate Test specimens were obtained by coating glass plates (38 mm long x 42 mm wide x approximately 180 μm thick) with the epoxy resin compositions of the examples and comparative examples to thicknesses of approximately 50 μm and approximately 100 μm, respectively, and heating them in a forced-air dryer at 150°C for 30 minutes. For the obtained test specimens, the maximum displacement was measured from the back side (glass plate side) using a surface roughness meter (Surfcom 480B, manufactured by Tokyo Seimitsu Co., Ltd.) and this was defined as the warpage amount. Furthermore, the horizontal axis was plotted with the thickness of the epoxy resin composition and the vertical axis with the warpage amount, and the slope of the approximate straight line was determined and defined as the warpage slope. The results are listed in Table 1 under "Warpage Slope (Warpage / Film Thickness)". 【0077】 In this evaluation, when the curvature slope is above a certain value (for example, 0.3 or more), the epoxy resin composition used exhibits sufficient curvature even in small amounts during curing. From this, it can be concluded that when bonding components such as LIDs and stiffeners to a semiconductor chip-mounted substrate that has experienced curvature, using only a small amount of epoxy resin composition provides sufficient stress to the substrate to counteract the curvature, thereby reducing the curvature (strain) of the substrate. 【0078】 - Maximum package strain A substrate (55 mm long x 55 mm wide x 0.97 mm thick) was prepared by mounting a Si chip (20 mm long x 20 mm wide x 725 μm thick) and sealing it with U8410-302 (underfill material for flip chips, manufactured by Namics Corporation). The maximum displacement 1 of the substrate was measured using a surface roughness meter (Surfcom 480B, manufactured by Tokyo Seimitsu Co., Ltd.). Next, the epoxy resin compositions of the examples and comparative examples were applied around the Si chip, a ring stiffener (outer circumference 55 mm x inner circumference 48.5 mm, thickness 0.5 mm, ring width 6.5 mm) was placed on the epoxy resin composition, and the specimen was heated at 150°C for 30 minutes using a forced-air dryer to obtain a test piece. The amount of epoxy resin composition applied was approximately 0.063 cm. ３The test specimen was passed through a reflow oven at a maximum temperature of 260°C three times, and then the maximum displacement 2 was measured from the back side (substrate side) of the test specimen using a surface roughness meter (Surfcom 480B, manufactured by Tokyo Seimitsu Co., Ltd.). The difference between the maximum displacement 2 and the maximum displacement 1 (= "maximum displacement 1" - "maximum displacement 2") is recorded in "Package Distortion Reduction (μm)" in Table 1. 【0079】 The package distortion reduction amount (μm) is an indicator of how much the epoxy resin composition was able to reduce the warping (distortion) of the substrate. For example, while a correction of 28 μm was achieved in Example 1, the comparative example showed a reduction of -20 μm, meaning that the warping actually worsened. In epoxy resin compositions, if the package distortion reduction amount is 10 μm or more, it can be evaluated that the warping of the substrate during the final curing stage can be suppressed. 【0080】 【0081】 The epoxy resin composition of the present invention exhibits excellent temporary adhesion and can suppress substrate warping during full curing. Therefore, semiconductor packages obtained by using the above epoxy resin composition as an adhesive can be manufactured with high reliability and high productivity. 【0082】 1 Semiconductor chip mounted substrate 2 Epoxy resin composition 3 Semiconductor chip 4 Encapsulating material 5 Substrate 10 Semiconductor chip mounted substrate 11 Semiconductor chip 12 Adhesive 13 Encapsulating material 14 Component (LID) 15 Epoxy resin composition 16 Substrate 21 Semiconductor chip 22 Encapsulating material 23 Epoxy resin composition 24 Substrate 25 Component (LID) 26 Cured product 27 Force

Claims

1. An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), a latent curing catalyst (C), and an inorganic filler (D), wherein the molar ratio of reactive groups contained in the curing agent (B) to epoxy groups contained in the epoxy resin (A) is 0.35 to 0.85, the content of the latent curing catalyst (C) relative to the resin component (100% by mass) in the composition is 10 to 16% by mass, and the content of the inorganic filler (D) is 35 to 67% by mass.

2. The epoxy resin composition according to claim 1, comprising an amine-epoxy adduct type latent curing catalyst (C) as the latent curing catalyst (C).

3. The epoxy resin composition according to claim 1 or 2, comprising a phenolic curing agent as the curing agent (B).

4. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) comprises at least one selected from the group consisting of bisphenol-type epoxy resins, cyclohexane-type epoxy resins, and aliphatic epoxy resins.

5. The epoxy resin composition according to claim 1 or 2, further comprising a silane coupling agent (E).

6. The epoxy resin composition according to claim 1 or 2, which is an adhesive for LID or stiffener.

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