Resin composition, semiconductor device, and method for manufacturing the same.

Abstract

Provided is a resin composition that is used as a capillary underfill (CUF) capable of further reducing filament cracking.　Provided is a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a filler. A cured product of this resin composition has a stress intensity factor range ΔKth for the fatigue crack propagation lower limit of 0.55 MPa∙m0.5 or greater.

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition. More specifically, the present disclosure relates to a resin composition used as a semiconductor encapsulating material, particularly a capillary underfill material (CUF: Capillary Underfill), a semiconductor device using the resin composition, a method for manufacturing the semiconductor device, and a method for manufacturing the resin composition. [Background Art]

[0002] In flip-chip connection, BGA (Ball Grid Array), or CSP (Chip Size Package) mounting, stress or strain due to curing may accumulate in the portion where the underfill material oozes out (fillet) around semiconductor elements or other electronic components, or in the bump joints. In this case, peeling or cracking may occur due to thermal shock, thermal expansion and contraction, moisture absorption, deformation accompanying heat treatment, or the like. Therefore, there arises a problem that peeling or cracks occurring in the fillet portion or the bump joint portion greatly affect the connection reliability between bump bonding sites, etc.

[0003] Furthermore, the solder used for forming bumps has been replaced with lead-free solder. Therefore, thermal stress increases as the reflow temperature during mounting becomes higher. Lead-free solder is inferior in mechanical strength to eutectic solder. In addition, the adoption of copper pillar bumps has reduced the application volume of lead-free solder. As a result, the mechanical strength is further reduced.

[0004] From the above, conventional underfill materials have a problem that peeling or cracking of the fillet portion, peeling or cracking of the bump joint portion, and the like are likely to occur.

[0005] Furthermore, as the number of bumps increases, the bump pitch and bump height decrease. As a result, gap narrowing is progressing. Also, along with higher integration, larger-sized chips are being employed. Therefore, underfill materials (CUF) are also required to have the property of being able to flow over a large area even in narrow gaps.

[0006] To address such problems, attempts have been made to reduce the stress and increase the toughness of underfill materials (CUF) (see Patent Document 1). PRIOR ART DOCUMENT PATENT DOCUMENT

[0007] Patent Document 1 Japanese Unexamined Patent Publication No. 2013-163747 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0008] In recent years, for underfill materials, there has been an increasing demand for suppressing the occurrence of cracks in the fillet portion described above. That is, there is a demand for an underfill material excellent in fillet crack resistance. Conventional techniques cannot sufficiently satisfy the above required properties. Therefore, further improvement has been required.

[0009] An object of the present disclosure is to provide a resin composition used as an underfill material (CUF) having more excellent fillet crack resistance in order to address the above-mentioned problems in the conventional technology. Furthermore, an object of the present disclosure is to provide a semiconductor device using the resin composition, a method for manufacturing the semiconductor device, and a method for manufacturing the resin composition. MEANS FOR SOLVING THE PROBLEM

[0010] In order to achieve the above object, the resin composition according to the present embodiment is (A) an epoxy resin, (B) a curing agent, (C) A resin composition comprising a filler, The cured product of the aforementioned resin composition is 0.55 MPa·m 0.5 The above fatigue crack propagation lower limit stress intensity factor range ΔK th It has.

[0011] The resin composition according to this embodiment preferably has a glass transition temperature (Tg) of 100°C or higher.

[0012] In the resin composition according to this embodiment, it is preferable that the epoxy resin (A) above includes a liquid epoxy resin.

[0013] In the resin composition according to this embodiment, it is preferable that the epoxy resin (A) above comprises at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and cyclohexane type epoxy resin.

[0014] In the resin composition according to this embodiment, the content of the above (C) filler is preferably 40 to 80 parts by mass with respect to 100 parts by mass of the total mass of all components of the resin composition.

[0015] In the resin composition according to this embodiment, the average particle size of the above (C) filler is preferably 0.1 to 20.0 μm.

[0016] In the resin composition according to this embodiment, it is preferable that the above-mentioned (C) filler is surface-treated with a silane coupling agent.

[0017] The resin composition according to this embodiment may further contain (D) core-shell rubber.

[0018] The resin composition according to this embodiment preferably satisfies requirement 1 described later in the cured product.

[0019] The resin composition according to this embodiment preferably satisfies requirement 2 described later in the cured product.

[0020] The semiconductor device according to this embodiment comprises a substrate, a semiconductor element disposed on the substrate, and a cured product of the resin composition according to this embodiment that encapsulates the semiconductor element.

[0021] The method for manufacturing a semiconductor device according to this embodiment includes filling the gap between a substrate and a semiconductor element disposed on the substrate with the resin composition according to this embodiment, and curing the resin composition.

[0022] The method for producing the resin composition according to this embodiment is a method for producing the resin composition described above, and includes producing the resin composition by mixing the (A) epoxy resin, the (B) curing agent, and the (C) filler using a roll mill, wherein the inter-roll pressure of the roll mill is 3.0 MPa or higher. [Effects of the Invention]

[0023] The underfill material (CUF) using the resin composition according to this embodiment has superior fillet crack resistance. [Brief explanation of the drawing]

[0024] [Figure 1] Figure 1 is a top view of a specimen used to measure the fatigue crack propagation limit stress intensity factor range ΔKth. [Figure 2] Figure 2 is a diagram illustrating the method of image analysis of the cross-section of a test specimen. [Modes for carrying out the invention]

[0025] The resin composition according to this embodiment will be described in detail below. The resin composition according to this embodiment contains the following components (A) to (C) as essential components.

[0026] (A) Epoxy resin The epoxy resin of component (A) is the main component of the resin composition according to this embodiment. The epoxy resin of component (A) preferably includes a liquid epoxy resin that is liquid at room temperature (25°C) from the viewpoint of viscosity and injectability. Epoxy resins that are solid at room temperature but exhibit a liquid state as a mixture when used in combination with a liquid epoxy resin can also be suitably used.

[0027] Examples of epoxy resins of component (A) include 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, glycidylamine type epoxy resin having an aromatic structure, and having an aromatic structure. Examples include glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins having an aromatic structure, epoxy resins having a butadiene structure having an aromatic structure, alicyclic epoxy resins having an aromatic structure, heterocyclic epoxy resins, spiro ring-containing epoxy resins having an aromatic structure, cyclohexanedimethanol type epoxy resins having an aromatic structure, naphthylene ether type epoxy resins, trimethylol type epoxy resins having an aromatic structure, tetraphenylmethane type epoxy resins, aminophenol type epoxy resins, and silicone-modified epoxy resins.

[0028] The epoxy resin of component (A) is preferably at least one resin selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and cyclohexane type epoxy resin.

[0029] Specific examples of liquid epoxy resins include "YDF8170" (bisphenol F type epoxy resin), "YDF8125" (bisphenol A type epoxy resin), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) from Nippon Steel Chemical & Material Co., Ltd., "HP-4032", "HP-4032D", "HP-4032SS" (naphthalene type epoxy resin) from DIC Corporation, and "jER828US", "jER828EL" (bisphenol A type epoxy resin), "jER806", "jER807" (bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation. Examples include "Nol-F type epoxy resin," "jER152" (phenol novolac type epoxy resin), "jER630," "jER630LSD" (aminophenol type epoxy resin), "YX7400" (high-rebound epoxy resin), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) from Nagase ChemteX Corporation, and "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) from Daicel Corporation.

[0030] Specific examples of solid epoxy resins include DIC's "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (dicyclopentadiene-type epoxy resin), "EXA7311", "EXA "7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin), "NC-7000-L" (naphthol novolac type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", "NC-3100" (biphenyl type epoxy resin), Nippon Steel Chemical & Material Co., Ltd.'s "ESN475V" (naphthol type epoxy resin), "ESN4 85 (Naphthol novolac type epoxy resin), Mitsubishi Chemical's "YX4000H", "YL6121" (Biphenyl type epoxy resin), "YX4000HK" (Bixylenol type epoxy resin), "YL7760" (Bisphenol AF type epoxy resin), "YX8800" (Anthracene type epoxy resin), Osaka Gas Chemical's "PG-100", "CG-500", Mitsubishi Chemical's "YL7800" (Fluorene type epoxy resin), Mitsubishi Chemical's "jER1010" (Solid bisphenol A type epoxy resin) Examples include (a type of epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "jER157S70" (bisphenol novolac type epoxy resin), "YX4000HK" (bixylenol type epoxy resin) and "YX8800" (anthracene type epoxy resin) from Mitsubishi Chemical Corporation, "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) from Mitsubishi Chemical Corporation, and "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation.

[0031] The epoxy resin of component (A) can be used alone, or two or more epoxy resins may be used in combination. The amount of epoxy resin component (A) is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, based on 100 parts by mass of the total mass of all components of the resin composition.

[0032] (B) Hardener The curing agent for component (B) is not particularly limited as long as it is a curing agent for epoxy resins. Known curing agents can be used. Examples of curing agents for component (B) include amine-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, hydrazide-based curing agents, polymercaptan-based curing agents, and Lewis acid-amine complexes. The curing agent of component (B) is preferably at least one curing agent selected from the group consisting of amine-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents.

[0033] Examples of amine-based curing agents include aliphatic amines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylenediamine, and 2-methylpentamethylenediamine; alicyclic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane; piperazine-type heterocyclic aliphatic amines such as N-aminoethylpiperazine and 1,4-bis(2-amino-2-methylpropyl)piperazine; and aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, dimethylthiotoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, and 4,4'-diamino-3,3'-diethyldiphenylmethane. Among these, 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, and dimethylthiotoluenediamine are preferred.

[0034] The acid anhydride-based curing agent is not particularly limited. Examples of acid anhydride-based curing agents include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, arachidized tetrahydrophthalic anhydride, methylhymic anhydride, succinic anhydride substituted with alkenyl groups, and glutaric anhydride. In particular, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic acid anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-1,2,3,6-tetrahydrophthalic acid anhydride, 1-isopropyl-4-methyl-bicyclo[2.2.2]octo-5-ene-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, hydrogenated methylnadic acid anhydride, alkenyl group-substituted succinic acid anhydride, and diethylglutaric acid anhydride are preferred.

[0035] Phenolic curing agents refer to monomers, oligomers, and polymers in general that have phenolic hydroxyl groups. Examples of phenolic curing agents include phenol novolac resins and their alkylated or allylated derivatives, cresol novolac resins, phenol aralkyl (including phenylene and biphenylene skeletons) resins, naphthol aralkyl resins, triphenolmethane resins, and dicyclopentadiene-type phenolic resins. Among these, allylphenol novolac resins are preferred.

[0036] The hardener of component (B) can be used alone. Alternatively, two or more hardeners may be used in combination.

[0037] The curing agent of component (B) is formulated such that the stoichiometric equivalent ratio (equivalent of curing agent / equivalent of epoxy groups) of the curing agent of component (B) and the epoxy resin of component (A) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. Furthermore, if the curing agent is a compound containing active hydrogen, such as an amine-based curing agent, the ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the epoxy resin (active hydrogen equivalent / epoxy equivalent) is preferably within the above range.

[0038] (C) Filler The filler of component (C) is not particularly limited, as long as it has the effect of lowering the coefficient of thermal expansion when added. Examples of fillers for component (C) include silica (silicon dioxide) filler, alumina (aluminum oxide) filler, and aluminum nitride filler. Silica (silicon dioxide) filler is particularly preferred because it allows for a high filling amount. The filler of component (C) may be surface-treated with, for example, a silane coupling agent.

[0039] The average particle size of the filler in component (C) is preferably 0.1 to 20.0 μm, more preferably 0.3 to 10.0 μm. Furthermore, in order to adjust the viscosity of the resin composition according to this embodiment, two or more fillers having different average particle sizes may be used in combination.

[0040] The shape of the filler in component (C) is not particularly limited. The shape of the filler in component (C) may be spherical, amorphous, or flaky, among other things. The filler of component (C) can be used alone, or two or more fillers may be used in combination. The amount of filler component (C) is preferably 40 to 80 parts by mass, more preferably 40 to 75 parts by mass, based on 100 parts by mass of the total mass of all components of the resin composition.

[0041] The resin composition according to this embodiment may contain, in addition to the above components (A) to (C), the components described below as necessary.

[0042] (D): Core shell rubber The resin composition according to this embodiment may also contain core-shell rubber as component (D). In the resin composition according to this embodiment, the core-shell rubber as component (D) is used for the purpose of suppressing the occurrence and propagation of fillet cracks when the resin composition is used as an underfill material (CUF). Specifically, when the resin composition according to this embodiment is used as an underfill material (CUF), the inclusion of component (D) (core-shell rubber) reduces the elastic modulus. This reduces the stress generated in the fillet portion. Therefore, the occurrence of fillet cracks can be suppressed. Furthermore, if a fillet crack occurs, the core-shell rubber component (D) acts as a stress reliever. Therefore, the propagation of the fillet crack can be suppressed.

[0043] In this specification, core-shell rubber refers to a multilayer rubber material composed of rubber particles forming a core and one or more shell layers covering it. As described later, the core of the core-shell rubber can be made of a material with excellent flexibility. At the same time, the shell layers of the core-shell rubber can be made of a material with excellent affinity for components other than component (D) contained in the resin composition, particularly epoxy resin as component (A). This makes it possible to achieve a low modulus of elasticity through the blending of rubber components while also achieving good dispersibility in the resin composition.

[0044] The rubber particles forming the core are made from materials with excellent flexibility. Examples of these materials include silicone-based rubber, butadiene-based rubber, styrene-based rubber, acrylic-based rubber, polyolefin-based rubber, and silicone / acrylic-based composite rubber.

[0045] On the other hand, as the constituent material of the shell layer, a material with excellent affinity for components other than component (D) contained in the resin composition according to this embodiment is used, particularly the epoxy resin as component (A). Examples of these constituent materials include acrylic resins, as well as epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins.

[0046] Specific examples of core shell rubber include Kaneka Corporation's "Kaneace MX-153", "Kaneace MX-257", "Kaneace MX-154", "Kaneace MX-960", "Kaneace MX-136", "Kaneace MX-137", "Kaneace MX-965", "Kaneace MX-217", "Kaneace MX-227M75", "Kaneace MX-334M75", "Kaneace MX-416", and "Kaneace MX-451", and Mitsubishi Chemical Corporation's "Metablen C-223A", "Metablen C-140A", "Metablen E-860A", "Metablen E-870A", "Metablen E-875A", "Metablen S-2100", "Metablen S-2200", and "Metablen Examples include "S-2260", "Stafyroid IM-203", "Stafyroid IM-401", "Stafyroid IM-601", "Stafyroid AC3355", and "Stafyroid AC3816" from Aica Kogyo Co., Ltd., and "Acryset BPA328" and "Acryset BPF307" from Nippon Shokubai Co., Ltd. In particular, silicone-based and butadiene-based cores are preferably used from the viewpoint of toughness, heat resistance, durability, and crack resistance.

[0047] The core-shell rubber of component (D) can be used alone. Alternatively, two or more types of core-shell rubber may be used in combination. The amount of core-shell rubber component (D) is preferably 0.3 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, based on 100 parts by mass of the total mass of all components of the resin composition.

[0048] (E): Curing accelerator The resin composition according to this embodiment may contain a curing accelerator as component (E). The curing accelerator as component (E) is not particularly limited as long as it is a curing accelerator for epoxy resins. Known curing accelerators can be used. The curing accelerator as component (E) imparts an appropriate curing rate to the epoxy resin as component (A). Examples of curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Examples of commercially available products include 2-phenyl-4-methylimidazole (manufactured by Shikoku Chemicals, trade name: 2P4MZ) and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (manufactured by Shikoku Chemicals, trade name: 2MZA). Alternatively, encapsulated imidazoles, also known as microencapsulated imidazoles or epoxy adduct imidazoles, may be used. Examples of encapsulated imidazoles include HX3941HP, HXA3942HP, HXA3922HP, HXA3792, HX3748, HX3721, HX3722, HX3088, HX3741, HX3742, and HX3613 (all manufactured by Asahi Kasei Chemicals, trade names), PN-23J, PN-40J, and PN-50 (manufactured by Ajinomoto Fine Techno, trade names), and FXR-1121 (manufactured by Fuji Kasei Kogyo, trade name). The curing accelerator of component (E) can be used alone. Alternatively, two or more curing accelerators may be used in combination. The amount of curing accelerator component (E) is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, based on 100 parts by mass of the total mass of all components of the resin composition.

[0049] (Other combination drugs) The resin composition according to this embodiment may further contain components other than components (A) to (E) as additional compounding agents, as needed. Examples of such compounding agents include coupling agents, ion trapping agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants, and reactive diluents. The amount of each compounding agent can be determined according to conventional methods.

[0050] Examples of coupling agents include silane coupling agents such as vinyl, glycidoxy, methacrylic, amino, mercapto, and imidazole types; titanium coupling agents such as alkoxide, chelate, and acylate types; and various long-chain spacer type coupling agents such as glycidoxyoctyltrimethoxysilane and methacrylooctyltrimethoxysilane. The coupling agents described above can be used alone, or two or more coupling agents may be used in combination.

[0051] (Preparation of resin composition) The resin composition according to this embodiment can be manufactured by conventional methods. For example, the resin composition is prepared by mixing components (A) to (C), and, if necessary, components (D), (E), or the other compounding agents mentioned above. If component (A) is a solid epoxy resin, preferably, component (A) is liquefied or fluidized by heating or the like before being mixed with the other components. If it is difficult to uniformly disperse the filler of component (C) in the epoxy resin of component (A), the epoxy resin of component (A) and the filler of component (C) may be mixed first, and then the remaining components may be mixed in afterward. When mixing the components, they can be mixed simultaneously. Alternatively, some components can be mixed first, and the remaining components can be mixed afterward. The method of mixing components (A) to (C) is not particularly limited. Known mixing methods can be used. In particular, ΔK, which will be described later, th A roll mill is preferably used because it allows for easy adjustment. Specifically, components (A) to (C), and optionally components (D), (E), and the other compounding agents are mixed using a roll mill. In this way, a resin composition can be suitably manufactured. A roll mill is preferably composed of three or more rolls. The pressure between rolls in a roll mill is not particularly limited. ΔK thThe inter-roll pressure is preferably 2 MPa or higher, more preferably 3 MPa or higher, as it is easier to adjust it within a predetermined range. The upper limit of the inter-roll pressure is not particularly limited. In many cases, the upper limit of the inter-roll pressure is 30 MPa or less. More often, the upper limit of the inter-roll pressure is 20 MPa or less.

[0052] The properties of the resin composition according to this embodiment will be described below. (Fatigue crack propagation limit stress intensity range ΔK) th ) Fatigue crack propagation limit stress intensity factor range ΔK th This is known as an index for evaluating fatigue crack propagation performance (lower limit stress intensity factor range ΔK). th A study on a simple identification method for [unclear], Koji Murakami, Koji Goto, Transactions of the Japan Welding Society, Vol. 35, No. 4, pp. 149-153 (2017), Japanese Patent Publication No. Hei 6-82353).

[0053] In fatigue crack propagation tests, the crack propagation velocity da / dN, which is determined from the relationship between the number of repeated load cycles N and the crack length a, is given as a function of the stress intensity factor width ΔK. The stress intensity factor K is expressed by the following formula. K=f(a / W)σ(πa) 1 / 2 Here, W is the width of the specimen, a is the crack length, σ is the applied stress, and f is a constant determined by the ratio of a to W. Specifically, the above value f is calculated using the following formula.

[0054]

number

[0055] A fatigue crack propagation test can be performed according to the procedure described later. When the relationship between the crack propagation velocity da / dN obtained from the test results and the stress intensity factor width ΔK is plotted, it can be seen that when the stress intensity factor width ΔK is below a certain value, the crack propagation velocity da / dN becomes 0, and fatigue cracks do not grow. This specific value is typically the lower limit stress intensity factor range for fatigue crack propagation, ΔK.th is defined as. When the stress intensity factor range ΔK is equal to or greater than the fatigue crack propagation threshold stress intensity factor range ΔK th , the crack propagation rate da / dN increases as the stress intensity factor range ΔK increases. At this time, the relationship between logda / dN and logΔK is substantially linear. It is known that the Paris law, expressed by the following formula, holds for this relationship. da / dN=C·ΔK^m However, in the present disclosure, when da / dN=1.0×10 -9 m / cycle, ΔK is defined as the fatigue crack propagation threshold stress intensity factor range ΔK th .

[0056] The fatigue crack propagation threshold stress intensity factor range ΔK of the cured product of the resin composition according to the present embodiment th is 0.55 MPa·m 0.5 or more. If ΔK th is 0.55 MPa·m 0.5 or more, fillet crack resistance is improved. Among these, ΔK th is preferably 0.56 MPa·m 0.5 or more, more preferably 0.60 MPa·m 0.5 or more. The upper limit of ΔK th is not particularly limited. In many cases, the upper limit is 0.9 MPa·m 0.5 or less. In more cases, this upper limit is 0.8 MPa·m 0.5 or less. ΔK th can be adjusted, for example, by the items described in (1) to (5) below. Note that ΔK th can be adjusted with only one of the following items (1) to (5). Alternatively, ΔK th can be adjusted by combining two or more items.

[0057] (1) Glass transition temperature (Tg) of the cured product of the resin composition ΔK th can be adjusted by the glass transition temperature (Tg) of the cured product of the resin composition. The lower the glass transition temperature (Tg) of the cured product of the resin composition described below, the higher ΔK thThe Tg tends to increase (see, for example, Examples 1 and 6 described later). A lower Tg reduces the crosslinking density of the resin skeleton. Therefore, flexibility increases. As a result, the stress on the cured resin composition can be relieved more. In this way, ΔK th It is thought that this can be made larger. The preferred range for the glass transition temperature (Tg) of the cured resin composition will be discussed later.

[0058] (2) Amount of ingredient (C) filler ΔK th This can be adjusted by the amount of filler in component (C). The higher the amount of filler in component (C), the higher the ΔK th The ratio tends to increase (see, for example, Examples 1 and 2 described later). By incorporating a large amount of filler, the elastic modulus and strength of the cured resin composition are improved. Therefore, the energy required for crack propagation per unit area increases. In this way, ΔK th It is thought that this can be made larger.

[0059] (3) Compounding of the core shell rubber of component (D) ΔK th This can also be adjusted by the compounding of the core-shell rubber component (D). When the core-shell rubber component (D) is compounded, ΔK th The ΔK tends to increase (see, for example, Examples 4 and 9 described later). The core-shell rubber relieves the stress on the cured resin composition, th It is thought that this can be made larger.

[0060] (4) Use of epoxy resin with a flexible skeleton as component (A) ΔK th This can also be adjusted by using an epoxy resin with a flexible skeleton as the epoxy resin of component (A). When an epoxy resin with a flexible skeleton is used as the epoxy resin of component (A), ΔK thΔK tends to increase (see, for example, Examples 1 and 7 described later). The flexible skeleton in the epoxy resin relieves the stress on the cured product of the resin composition, th It is thought that this can be made larger. Here, a flexible skeleton refers to a molecular skeleton, such as an alkyl chain or siloxane, that has a structure that allows for easy movement. Examples of epoxy resins with a flexible skeleton include (poly)alkylene glycol-modified epoxy resins such as (poly)ethylene glycol-modified epoxy resins, (poly)propylene glycol-modified epoxy resins, (poly)tetramethylene glycol-modified epoxy resins, and (poly)hexamethylene glycol-modified epoxy resins. Other examples include epoxy resins with a siloxane skeleton, such as bis(2-(3,4-epoxycyclohexyl)ethyl)polydimethylsiloxane and polydimethylsiloxane diglycidyl ether, as well as polyisobutylene diglycidyl ether.

[0061] (5) Uniformity of the resin composition ΔK th This can also be adjusted by the uniformity of the composition in the resin composition. When the resin composition is kneaded using a three-roll mill under high pressure, ΔK th The stress tends to increase (see, for example, Example 3 and Comparative Example 5 described later). If the composition of the resin composition is non-uniform, stress concentrates in one place in the cured resin composition. Then, cracks are more likely to propagate from that point. By making the composition of the resin composition uniform, stress is evenly propagated inside the cured resin composition. In this way, we believe that the strength of the cured resin composition can be maximized.

[0062] The above ΔK th When measuring, the resin composition according to this embodiment is first subjected to a curing treatment. This yields a test specimen. In the curing treatment, the applied resin composition is heat-treated at 165°C for 2 hours. The test specimen is prepared by the heat treatment described above. The size of the test specimen is 20 mm (L) × 2 mm (W) × 0.5 mm (T). A crack (length 0.3 mm) was pre-formed in the test specimen. More specifically, Figure 1 is a top view of the test specimen 10. In Figure 1, a surface consisting of length L and width W is observed. As shown in Figure 1, a crack 12 is formed in the center of length L of the test specimen 10, extending from one side to the other. The direction in which the crack 12 extends is parallel to the width direction of the test specimen 10. The crack 12 is formed so as to penetrate the test specimen in the thickness direction. In the test described later, stress will be applied to the test specimen in the direction indicated by the arrow. A micro-load testing machine (Sagimiya Seisakusho: LMH207-10) is used to apply repeated loads (stresses). A microscope (Olympus: SZX-16) and a time-lapse video / still image acquisition system are used for crack observation. The load waveform from the micro-load testing machine is a sine wave with a frequency of 2 Hz. However, the fatigue crack propagation lower limit stress intensity factor range ΔK is not specified. th Due to its characteristics, the test is preferably conducted at low stress to confirm the crack propagation behavior under minute stresses. The test stress is then gradually increased only if no crack propagation occurs. Therefore, the test is conducted by first applying a load repeatedly to the specimen while changing the value of X under the load conditions of one cycle, where the load waveform is a sine wave, the frequency is 2 Hz, the minimum stress is 0 (N), and the maximum stress is X (N). In this way, the value of X at which no crack of 1 μm or more propagates after 20,000 cycles is found. Next, the load is repeatedly applied to the specimen while increasing the value of X by 0.1 N each time from the found value of X. Then, the minimum value of X at which a crack of 1 μm or more propagates after 20,000 cycles (hereinafter also referred to as "value Y") is determined. For example, first, under the above load conditions, a cyclic load is applied to the test specimen with a maximum stress X of 14 (N). If no cracks of 1 μm or more propagate after 20,000 cycles, then the cyclic load is applied to the test specimen under the same load conditions again, but with a maximum stress X of 14.1 (N), which is 0.1 (N) higher than the previous value. After 20,000 cycles, it is checked whether cracks of 1 μm or more have propagated. If no cracks have propagated, the same test is performed with a maximum stress X of 14.2 (N), which is 0.1 (N) higher than the previous value. In this way, the test is repeated with a maximum stress X that is increased by 0.1 (N) increments until crack propagation of 1 μm or more is confirmed after 20,000 cycles. This allows the minimum value Y of the maximum stress X to be determined. Next, under the condition that X is value Y, a repeated load is applied to the specimen. At this time, crack propagation is observed on the surface of the specimen, which consists of length L and width W. The length Lc of this crack (see Figure 1) is measured. Then, the relationship between the crack propagation velocity da / dN and the stress intensity factor width ΔK is plotted. Here, da / dN = 1.0 × 10⁻⁶ -9 ΔK is ΔK when m / cycle th It is defined as follows. Note that the stress intensity factor range ΔK is the maximum value ΔK of the stress intensity factor K during one cycle. max and minimum value ΔK min This corresponds to the difference between the two. Here, in the above measurement, the minimum stress value ΔK during one cycle is min ΔK = ΔK max The relationship can be obtained.

[0063] (Glass transition temperature (Tg)) The glass transition temperature (Tg) of the cured resin composition according to this embodiment is preferably 100°C or higher. The underfill material preferably has good bump crack resistance in addition to good fillet crack resistance. Bump crack resistance is improved when the Tg is 100°C or higher. The Tg of the cured resin composition according to this embodiment is more preferably 103°C or higher, and even more preferably 105°C or higher. There is no particular upper limit to the Tg of the cured resin composition according to this embodiment. In many cases, this upper limit of Tg is 200°C or lower. More often, this upper limit of Tg is 180°C or lower. To measure the glass transition temperature described above, a test specimen is first obtained by curing the resin composition according to this embodiment. The curing process involves heating the coated resin composition at 165°C for 2 hours. The resulting cured film thickness is adjusted to be within the range of 2000 ± 100 μm. Next, the glass transition temperature of the obtained cured product can be determined using a dynamic thermomechanical analyzer (DMA) by the double-arm bending method under the conditions of -20 to 260°C, frequency of 1 Hz, and heating rate of 3°C / min. The glass transition temperature (Tg) can be determined from the peak temperature of the loss loss tangent (tanδ), which is obtained from the loss modulus (E'') / storage modulus (E').

[0064] (viscosity) The resin composition according to this embodiment has low viscosity. Therefore, when the resin composition is used as an underfill material (CUF), it exhibits good injectability by capillary flow. Specifically, the viscosity measured using a rotational viscometer at 25°C and a rotational speed of 50 rpm is preferably 100 Pa·s or less, more preferably 80 Pa·s or less. The lower limit is not particularly limited. In many cases, the lower limit is 1 Pa·s or more. More often, the lower limit is 10 Pa·s or more.

[0065] (Requirement 1) The cured product of the resin composition according to this embodiment preferably satisfies the following requirement 1. Requirement 1: In the cross-section of the cured resin composition, the area (μm) occupied by the filler in each of six randomly selected regions measuring 37.8 μm horizontally and 18.9 μm vertically. 2 When calculating the result, the standard deviation of the area of ​​each of the six fillers obtained (filler area) is 0.36 μm. 2 The following applies. Here, the filler area is obtained by observing the cross-section of the cured resin composition at a magnification of 1000x using a scanning electron microscope. The following details requirement 1.

[0066] In Requirement 1, the standard deviation of the filler area in the cross-section of the cured resin composition is calculated. The smaller this standard deviation, the more uniform the size and / or distribution of the fillers contained in the resin composition. In other words, a small standard deviation indicates high uniformity of the composition of the resin composition. That is, the standard deviation is related to the uniformity of the resin composition as described in (5) above. Therefore, the smaller the standard deviation calculated in Requirement 1, the higher ΔK th It becomes larger. The standard deviation calculated in Requirement 1 is preferably 0.36 μm. 2 More preferably 0.27 μm 2 The following applies. The lower limit of the above standard deviation is not particularly limited. In many cases, this standard deviation is 0 μm. 2 That's all. More often, this standard deviation is 0.02 μm. 2 That's all. The following details an example of how to calculate the standard deviation of the area occupied by the filler in Requirement 1.

[0067] First, a test specimen is obtained by curing the resin composition according to this embodiment. Specifically, a glass plate is first fixed to an organic substrate (FR-4 substrate) with a gap of 100 μm between them. The organic substrate with the fixed glass plate is then placed on a hot plate set to 110°C. The resin composition according to this embodiment is then injected into the gap. The injection width is 10 mm. The injection length is 20 mm. Subsequently, as a curing treatment, the injected resin composition is heat-treated at 165°C for 2 hours. Next, the obtained test specimen (cured resin composition) is fractured. The exposed cross-section at the injection distance of 10 mm is then observed. A scanning electron microscope (Hitachi Scanning Electron Microscope System S-3400N) is used for observation. The observation magnification is 1000x. The image size during observation is 122.4 μm horizontally and 93.4 μm vertically. The resolution is 1280 × 960. Next, the acquired observation images are analyzed using the image analysis software WinROOF2018 (Mitani Shoji Co., Ltd., Ver4.5.5). The range of the image analysis is 113.4 μm horizontally and 37.8 μm vertically within the acquired observation image. The pixel count is 1200 × 400. Specifically, to reduce noise, the cross-sectional observation image of the hardened material is filtered using a median filter (5 × 5 pixels) with the above software. Furthermore, the observation image is converted to a monochrome image, followed by binarization. In the binarization process, images with grayscale below a predetermined threshold are cut off. Images with grayscale above the threshold are treated as 1, and images with grayscale below the threshold are treated as 0. Binarization is performed using Otsu's method (discriminant analysis method). Next, the filler area (μm) in the 37.8 μm x 18.9 μm region of the binarized observation image. 2The average filler area (μm²) is calculated. The above 37.8 μm x 18.9 μm region corresponds to the 400 x 200 pixel region in the binarized observation image 20 in Figure 2 (the region labeled A in Figure 2). Specifically, the number of pixels contained in the filler in one region selected from regions A to F in Figure 2 is calculated. Then, that number of pixels is multiplied by the area of ​​one pixel. The resulting value is defined as the filler area. The filler area in each selected region is obtained using the above procedure. Furthermore, the average value of these six filler areas is calculated. The calculated average value is defined as the average filler area (μm²). 2 ) is defined as follows. Through the above process, the filler area is calculated for each of the six regions (regions A to F in Figure 2) in the binarized observation image 20 shown in Figure 2. The standard deviation is calculated using the six obtained filler area values. The obtained value is 0.36 μm. 2 Requirement 1 is met if the following conditions are met: In the above method, when the standard deviation is calculated, a region wider than 37.8 μm x 18.9 μm is binarized. However, the 37.8 μm x 18.9 μm region selected from regions A to F may itself be binarized. Subsequently, the filler area of ​​the selected region may be calculated using the above process. The standard deviation can also be determined by performing this process on six different locations. Furthermore, the six randomly selected regions corresponding to the standard deviations calculated above refer to six regions that do not overlap with each other. Furthermore, the number of pixels contained in the filler of each region measuring 37.8 μm horizontally and 18.9 μm vertically can be calculated. Then, the standard deviation of the number of pixels contained in the filler of each region (hereinafter also referred to as the "standard deviation of the number of pixels") can be calculated. In this case, the standard deviation of the number of pixels is preferably 40 pixels or less. There is no particular lower limit to the above standard deviation of the number of pixels. For example, the lower limit is 0 pixels.

[0068] (Requirement 2) The cured product of the resin composition according to this embodiment preferably satisfies the following requirement 2. Requirement 2: When calculating the number of fillers in each of six randomly selected regions measuring 37.8 μm x 18.9 μm in length on the cross-section of the cured resin composition, the standard deviation of the obtained number of fillers must be 80 or less. Here, the number of fillers is obtained by observing the cross-section of the cured resin composition at a magnification of 1000x using a scanning electron microscope. The following details requirement 2.

[0069] In Requirement 2, the standard deviation of the number of fillers in the cross-section of the cured resin composition is calculated. A smaller value for this standard deviation indicates higher uniformity of the resin composition. In other words, this standard deviation is related to the uniformity of the resin composition as described in (5) above. Therefore, the smaller the standard deviation in Requirement 2, the higher ΔK th The number of factors becomes larger. The standard deviation of requirement 2 is preferably 60 or less, more preferably 55 or less. There is no particular lower limit to the above standard deviation. In many cases, this standard deviation is 0 or more. More often, this standard deviation is 5 or more. The following details an example of how to calculate the standard deviation of the number of fillers in the sub-region where the fillers are located, as required by Requirement 2.

[0070] In calculating the standard deviation for Requirement 2, the binarized observation image is obtained by following the same procedure as described in Requirement 1. Next, the number of fillers in a region measuring 37.8 μm horizontally and 18.9 μm vertically within the binarized observation image is calculated. The above process calculates the number of fillers in each of the six regions (regions A to F in Figure 2) of the binarized observation image 20 shown in Figure 2. The standard deviation is calculated using the obtained values ​​of the number of fillers in the six regions. If the obtained value is 80 or less, requirement 2 is satisfied. In the above method, when the standard deviation is calculated, an observation image wider than a 37.8 μm x 18.9 μm area is binarized. However, the 37.8 μm x 18.9 μm area selected from areas A to F may itself be binarized. Subsequently, the number of fillers in the selected area may be calculated by the above process. The standard deviation may be obtained by performing this process on six different locations. Furthermore, the six randomly selected regions corresponding to the standard deviation calculated above refer to six regions that do not overlap with each other.

[0071] The semiconductor device according to this embodiment comprises a substrate, a semiconductor element disposed on the substrate, and a cured product of the resin composition according to this embodiment that encapsulates the semiconductor element. Semiconductor devices are not particularly limited. Examples of semiconductor devices include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors.

[0072] The method for manufacturing a semiconductor device according to this embodiment comprises filling the gap between a substrate and a semiconductor element disposed on the substrate with a resin composition according to this embodiment, and curing the resin composition.

[0073] In filling with the above-described resin composition, for example, the resin composition according to this embodiment is applied to one end of the semiconductor element while the substrate is heated to 70-120°C. Then, the void between the substrate and the semiconductor element is filled with the resin composition according to this embodiment by capillary action. At this time, the substrate may be tilted in order to shorten the time required for filling with the resin composition according to this embodiment. Alternatively, a pressure difference may be created inside and outside the void.

[0074] In the curing of the above resin composition, after the gap is filled with the resin composition according to this embodiment, the substrate is heated at a predetermined temperature for a predetermined time, for example, 150 to 165°C for 0.5 to 2 hours. In this way, the gap is sealed by the heat curing of the resin composition. [Examples]

[0075] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to these examples.

[0076] (Examples 1-13, Comparative Examples 1-5) The raw materials were kneaded using a roll mill (3-roll mill) according to the mixing ratios shown in the table below. In this way, the resin compositions of Examples 1-13 and Comparative Examples 1-5 were prepared. The pressure (pressure between rolls) during roll mill kneading was 3 MPa for all examples except Comparative Example 5, which was 1 MPa. The numerical values ​​for each composition in the table represent parts by mass.

[0077] The components used in the preparation of the resin composition are as follows:

[0078] Component (A): Epoxy resin Epoxy resin A-1: ​​Liquid bisphenol F type epoxy resin, product name YDF8170, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent weight 158 ​​g / eqs Epoxy resin A-2: Liquid aminophenol type epoxy resin, product name jER630, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 98 g / eq. Epoxy resin A-3: Liquid naphthalene-type epoxy resin, product name HP-4032D, manufactured by DIC Corporation, epoxy equivalent 140 g / eq Epoxy resin A-4: Liquid cyclohexane type epoxy resin, product name EP-4085S, manufactured by ADEKA, epoxy equivalent 145 g / eq

[0079] Ingredient (B): Hardener Curing agent B-1: Amine-based curing agent, 4,4'-diamino-3,3'-diethyldiphenylmethane, product name HDAA, active hydrogen equivalent 63.5 g / eq, manufactured by Nippon Kayaku Co., Ltd. Curing agent B-2: Amine-based curing agent, diethyltoluenediamine, product name EtaCure 100, active hydrogen equivalent 44.5 g / eq, manufactured by Albemarle. Curing agent B-3: Amine-based curing agent, dimethylthiotoluenediamine, product name EtaCure 300, active hydrogen equivalent 53.5 g / eq, manufactured by Albemarle. Curing agent B-4: Acid anhydride-based curing agent, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic acid anhydride, product name YH307, active hydrogen equivalent 117 g / eq, manufactured by Mitsubishi Chemical Corporation.

[0080] Ingredients (C): Filler Filler C-1:3-glycidoxypropyltrimethoxysilane surface-treated silicon dioxide, average particle size 0.5 μm, product name SE2200-SEJ, manufactured by Admatex Corporation. Filler C-2: Silicon dioxide, average particle size 0.5 μm, product name SO-E2, manufactured by Admatex Co., Ltd. Filler C-3:3-glycidoxypropyltrimethoxysilane surface-treated silicon dioxide, average particle size 1.5 μm, product name SE5050-SEJ, manufactured by Admatex Corporation. Filler C-4:3-glycidoxypropyltrimethoxysilane surface-treated silicon dioxide, product name SE1050-SEO, average particle size 0.3 μm, manufactured by Admatex. Filler C-5: Aluminum oxide, product name A9-SX-E2, average particle size 10 μm, manufactured by Admatex Corporation.

[0081] Component (D): Core shell rubber Core-shell rubber D-1: Product name MX-137 (Core-shell type butadiene rubber particles, manufactured by Kaneka Corporation) Core-shell rubber D-2: Product name MX-965 (Core-shell type silicone rubber particles, manufactured by Kaneka Corporation)

[0082] Ingredient (E): Curing accelerator Curing accelerator E-1: 2-phenyl-4-methylimidazole, product name 2P4MZ, manufactured by Shikoku Chemicals Co., Ltd.

[0083] (viscosity) The viscosity (Pa·s) of the evaluation sample immediately after preparation was measured using a Brookfield viscometer at a liquid temperature of 25°C and 50 rpm.

[0084] (Tg) The storage modulus and loss modulus of the cured resin compositions of each example and comparative example were measured using a dynamic viscoelastic apparatus. The peak value of tanδ, which is the ratio of these moduli, was measured as Tg. The above moduli were measured in accordance with the Japanese Industrial Standard JIS C6481. More specifically, first, spacers made of overlapping heat-resistant tape were placed at two locations on a Teflon® sheet attached to the surface of a 3 mm thick glass plate. At this time, the thickness of the spacers was adjusted so that the thickness of the cured resin composition, as described later, would be 2000 ± 100 μm. Next, the resin composition was applied to the Teflon sheet between the spacers. Taking care not to trap air bubbles, the applied resin composition was sandwiched between another glass plate with a Teflon® sheet attached to its surface. In this state, the resin composition was cured at 165°C for 2 hours. Finally, the cured material obtained in this way was peeled off the Teflon® sheet. After that, the cured material was cut to a predetermined size (10 mm × 50 mm) using a cutting machine. In this way, a test piece was obtained. The cut edges of the cured material were smoothed with sandpaper. The Tg of this specimen was measured using a dynamic thermomechanical analyzer (DMA) (manufactured by Hitachi High-Tech Science Corporation) under the conditions of -20 to 260°C, frequency of 1 Hz, and heating rate of 3°C / min, using the double-arm bending method. Tg was determined from the peak temperature (°C) of tanδ obtained from E'' / E'.

[0085] (ΔK th ) Follow these steps to ΔK th They sought it. A fatigue crack propagation test was conducted, and the stress intensity factor width ΔK, expressed by the following equation, was determined. ΔK = f(a / W)σ(πa) 1 / 2 W is the width of the specimen, a is the crack length, σ is the applied stress, and f is a constant determined by the ratio of a to W. Test specimens were prepared by curing the resin compositions of each example and comparative example at 165°C for 2 hours. The test specimen measured 20 mm (L) × 2 mm (W) × 0.5 mm (T). As explained in Figure 1, a crack 0.3 mm in length was created in the test specimen. A micro-load testing machine (Sagimiya Seisakusho: LMH207-10) was used as the testing apparatus. A microscope (Olympus: SZX-16) and a video / still image (time-lapse) long-term acquisition system were used for crack observation. The load waveform obtained by the micro-load testing machine was a sine wave. Its frequency was 2 Hz. Next, as described above, the test was repeated while changing the value of X under the load conditions of one cycle, where the load waveform is sinusoidal, the frequency is 2 Hz, the minimum stress is 0 (N), and the maximum stress is X (N). After 20,000 cycles of loading under the same load conditions, the minimum value of X at which crack propagation of 1 μm or more was observed in the specimen was determined. By repeatedly applying the load to the specimen with the determined minimum value, the relationship between the obtained crack propagation velocity da / dN and the stress intensity factor width ΔK was plotted. The obtained da / dN = 1.0 × 10⁻⁶ -9 ΔK is ΔK when m / cycle th It was defined as follows.

[0086] (Reliability testing) Test specimens, mounted on Walts-TEG FC150JY silicon chips on Walts-KIT FC150 01A150P-10 substrates manufactured by Walts, were coated with the resin compositions of each example and comparative example. The coated resin compositions were cured at 165°C for 2 hours. A preconditioning test was conducted under JEDEC Level 3 conditions. Subsequently, under Condition B conditions, Th A 1000-cycle emergency cycle was performed. Afterward, the fillet section was observed using a microscope to evaluate fillet crack resistance. In this way, the presence or absence of fillet cracks was observed. Furthermore, to evaluate bump crack resistance, a resistance meter was used to observe the presence or absence of breaks in the daisy chain within the test specimen. Reliability testing was performed five times using different test specimens.

[0087] In Tables 1-3, "Filler Addition Amount" represents the filler content (parts by mass) per 100 parts by mass of the resin composition. In Tables 1-3, "Rubber particle addition amount" represents the amount of core-shell rubber (parts by mass) per 100 parts by mass of the resin composition. In Tables 1-3, "Equivalent Ratio" represents the ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the epoxy resin (active hydrogen equivalent / epoxy equivalent). In Tables 1-3, "Fillet Crack" represents the number of specimens exhibiting fillet cracks in the reliability tests described above. For example, "0 / 5" means that no fillet cracks were observed in any of the specimens when the reliability tests described above were performed five times using different specimens. "1 / 5" means that fillet cracks were observed in one specimen. In Tables 1-3, "Poor Conductivity (Open)" represents the number of test specimens showing daisy-chain breakage in the reliability test described above. For example, "0 / 5" means that when the reliability test described above was performed five times using different test specimens, no daisy-chain breakage was observed in any of the specimens. "1 / 5" means that a daisy-chain breakage was observed in one test specimen. In Tables 1-3, "Pressure between rolls (MPa)" represents the pressure between rolls during a roll mill operation.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] 0.55 MPa·m 0.5 The above ΔK thNo fillet cracks were observed in any of Examples 1-13, which showed the above characteristics. The frequency of wire breakage was less than 1 in 5 trials. No wire breakage was observed in any of Examples 1-7 and 9-13, which showed a Tg of 105°C or higher. Note that in Examples 2 and 3, the filler formulation ratio was changed from that in Example 1. In Example 4, epoxy resins of two different components (A) are used in combination. Examples 5 and 6 are modified versions of Example 4, in which the equivalent ratio of component (A) epoxy resin and component (B) curing agent is changed. In Example 7, unlike in Example 4, epoxy resin A-4 is used in combination with epoxy resin A-1 instead of epoxy resin A-2 as component (A). In Example 8, the equivalent ratio of the epoxy resin component (A) and the curing agent component (B) in Example 7 has been changed. In Example 9, two different epoxy resin components (A) are used in combination. Furthermore, core-shell rubber component (D) is added to the composition. In Example 10, a different epoxy resin is used as component (A) than in Example 1. Furthermore, core-shell rubber, component (D), is added to the composition. In Example 11, epoxy resins with three different components (A) are used in combination. Furthermore, two different curing agents are used as component (B) compared to Example 1. In Example 12, a different curing agent is used as component (B) compared to Example 1. Furthermore, two different fillers are used in combination as component (C) compared to Example 1. In Example 13, a different curing agent is used as component (B) than in Example 1. Furthermore, a different filler is used as component (C) than in Example 1. 0.55 MPa·m 0.5 ΔK less than th Fillet cracks were observed in all of Comparative Examples 1 to 5, which had the specified characteristics.

[0092] (Evaluation of Requirement 1) The resin compositions of Examples 3, 10, 12, and Comparative Example 5 were used to evaluate Requirement 1 according to the procedure described below. Table 4 shows the results obtained. To evaluate Requirement 1, test specimens were first obtained by curing the resin compositions of Examples 3, 10, 12, and Comparative Example 5. Specifically, a glass plate was first fixed onto an organic substrate (FR-4 substrate) with a 100 μm gap between them. The organic substrate with the fixed glass plate was then placed on a hot plate set to 110°C. The resin compositions of Examples 3, 10, 12, and Comparative Example 5 were then injected into the gap. The injection width was 10 mm, and the injection length was 20 mm. Subsequently, as a curing treatment, the injected resin compositions were heat-treated at 165°C for 2 hours. The obtained test specimen (cured resin composition) was fractured. The exposed cross-section at the injection distance of 10 mm was then observed. A scanning electron microscope (Hitachi Scanning Electron Microscope System S-3400N) was used for observation. The observation magnification was 1000x. The image size during observation was 122.4 μm horizontally and 93.4 μm vertically. The resolution was 1280 × 960. Next, the acquired observation images were analyzed using the image analysis software WinROOF2018 (Mitani Shoji Co., Ltd., Ver4.5.5). The range of the image analysis was 113.4 μm horizontally and 37.8 μm vertically within the acquired observation images. The pixel count was 1200 × 400. The specific procedure for image analysis was as follows: To reduce noise, the cross-sectional observation images of the hardened material were filtered using the above software with a median filter (5 × 5 pixels). Furthermore, the observation images were converted to monochrome, and then binarized. In the binarization process, images with a grayscale below a predetermined threshold were cut off. Images with a grayscale above the threshold were assigned a value of 1, and images with a grayscale below the threshold were assigned a value of 0. Binarization was performed using Otsu's method (discriminant analysis). Next, the filler area (μm) in the 37.8 μm x 18.9 μm region of the binarized observation image. 2 The result was calculated. The above process was performed on six locations (see Figure 2) in the binarized observation image. In this way, the filler area of ​​each region was calculated. Using the six obtained filler area values, the standard deviation (standard deviation of area (μm)) was calculated. 2 The result was calculated. Note that the standard deviation of the area (μm) 2 Along with the above, the standard deviation of the average number of pixels was also calculated.

[0093] (Evaluation of Requirement 2) The resin compositions of Examples 3, 10, 12, and Comparative Example 5 were used to evaluate Requirement 2 according to the procedure shown below. To evaluate Requirement 2, first, binarized observation images were obtained, similar to the evaluation of Requirement 1 above. Next, the number of fillers in a 37.8 μm x 18.9 μm region of the binarized observation image was calculated. Through this process, the number of fillers in each of the six regions (see Figure 2) of the binarized observation image was calculated. Using the obtained values ​​for the number of fillers in the six regions, the standard deviation (standard deviation of the number of fillers) was calculated.

[0094] In Table 4, "Pressure between rolls (MPa)" represents the pressure between rolls during a roll mill. In Table 4, "Standard deviation of area (μm)" 2 ) is the standard deviation of the filler area calculated in the above (evaluation of requirement 1). In Table 4, "Standard deviation of area (number of pixels)" is the standard deviation of the average number of pixels mentioned above. In Table 4, "Standard deviation of number (number of pieces)" is the standard deviation of the number of fillers calculated as described above (evaluation of requirement 2).

[0095] [Table 4]

[0096] As shown in Table 4 above, the resin compositions of Examples 3, 10, and 12 satisfy requirements 1 and 2. These compositions were confirmed to exhibit excellent uniformity. It is believed that the desired effects were obtained by using resin compositions exhibiting such characteristics. [Explanation of symbols]

[0097] 10 test specimens 12 Cracks 20 Binarized observation images

Claims

1. (A) Epoxy resin, (B) Hardener, (C) A resin composition comprising a filler, The cured product of the resin composition has a pressure of 0.55 MPa·m ０．５ The above range of stress intensity factors for the lower limit of fatigue crack propagation ΔK ｔｈ It has, The epoxy resin (A) comprises at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and cyclohexane type epoxy resin. The content of the (C) filler is 40 to 80 parts by mass with respect to 100 parts by mass of the total mass of all components of the resin composition. The viscosity measured using a rotational viscometer at 25°C and a rotational speed of 50 rpm is 100 Pa·s or less. The cured product of the resin composition satisfies the following requirement 1: Resin composition. Requirement 1: Observe the cross-section of the cured resin composition with a scanning electron microscope at 1000x magnification, and determine the average area (μm) of the filler within a region of 37.8 μm x 18.9 μm. ２ When the operation to calculate the area of ​​the six fillers was performed at six randomly selected locations, the standard deviation of the areas of the six fillers obtained was 0.36 μm. ２ The following is

2. (A) Epoxy resin, (B) Hardener, (C) A resin composition comprising a filler, The cured product of the resin composition has a pressure of 0.55 MPa·m ０．５ The above range of stress intensity factors for the lower limit of fatigue crack propagation ΔK ｔｈ It has, The epoxy resin (A) comprises at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and cyclohexane type epoxy resin. The content of the (C) filler is 40 to 80 parts by mass with respect to 100 parts by mass of the total mass of all components of the resin composition. The viscosity measured using a rotational viscometer at 25°C and a rotational speed of 50 rpm is 100 Pa·s or less. The cured product of the resin composition satisfies the following requirement 2: Resin composition. Requirement 2: When the cross-section of the cured resin composition is observed at 1000x magnification using a scanning electron microscope and the number of fillers in a region of 37.8 μm x 18.9 μm is calculated at six randomly selected locations, the standard deviation of the number of fillers obtained from the six locations is 80 or less.

3. The glass transition temperature (Tg) of the cured product of the resin composition is 100°C or higher. The resin composition according to claim 1 or 2.

4. The epoxy resin (A) includes a liquid epoxy resin. The resin composition according to claim 1 or 2.

5. The average particle size of the (C) filler is 0.1 to 20.0 μm. The resin composition according to claim 1 or 2.

6. The (C) filler is surface-treated with a silane coupling agent. The resin composition according to claim 1 or 2.

7. Furthermore, (D) including core shell rubber, The resin composition according to claim 1 or 2.

8. The invention comprises a substrate, a semiconductor element disposed on the substrate, and a cured product of the resin composition according to claim 1 or 2 that encapsulates the semiconductor element. Semiconductor equipment.

9. The method includes filling the gap between the substrate and the semiconductor element disposed on the substrate with the resin composition described in claim 1 or 2, and curing the resin composition. A method for manufacturing a semiconductor device.

10. (A) Epoxy resin, (B) Hardener, (C) Filler, The cured material has a pressure of 0.55 MPa·m ０．５ The above range of stress intensity factors for the lower limit of fatigue crack propagation ΔK ｔｈ A method for producing a resin composition having the following characteristics: The method includes producing a resin composition by mixing (A) epoxy resin, (B) curing agent, and (C) filler using a roll mill. The inter-roll pressure of the aforementioned roll mill is 3.0 MPa or higher. A method for producing a resin composition.

11. The epoxy resin (A) comprises at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, and cyclohexane type epoxy resin. A method for producing the resin composition according to claim 10.

12. The content of the (C) filler is 40 to 80 parts by mass with respect to 100 parts by mass of the total mass of all components of the resin composition. A method for producing the resin composition according to claim 10 or 11.

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