Resin composition for electronic component and semiconductor device using the same

Abstract

To provide a resin composition for an electronic component allowing manufacture of a highly reliable electronic component under relatively low temperature conditions.SOLUTION: The foregoing problem is solved by a resin composition for an electronic component that comprises an epoxy compound that is liquid at 25°C and a thiol compound that is liquid at 25°C, and has a glass transition temperature of 80°C or more after heating at 80°C for 1 hour.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition for electronic parts and a semiconductor device using the same. [Background technology]

[0002] In recent years, there has been a demand for electronic devices to have higher speeds, lower power consumption, larger capacities, lower costs, etc., and particularly in the field of electronic components, there is a demand for finer and more multi-layered circuit boards, higher density packaging of device chips, etc. In the production of such electronic components, it has been proposed to use an epoxy resin composition containing an epoxy resin for fixing semiconductor members (e.g., semiconductor elements, semiconductor chips, etc.) to a substrate, sealing the semiconductor members, or filling voids that occur between the semiconductor members and the circuit board (e.g., Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2022 / 130575 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-248004 Summary of the Invention [Problem to be solved by the invention]

[0004] Here, when manufacturing electronic components, it is preferable to minimize the thermal history of semiconductor components. Meanwhile, when manufacturing electronic components, high-temperature processes such as soldering are usually required, and heat resistance is also required for various components. In contrast, the resin compositions described in Patent Documents 1 and 2 above must be heated to 150°C or higher for curing, and further improvements are needed to reduce the thermal history of semiconductor components and the like.

[0005] The present invention has been made in view of the above-mentioned problems, and specifically aims to provide a resin composition for electronic components that enables highly reliable electronic components to be produced at relatively low temperatures, and a semiconductor device using the same. [Means for solving the problem]

[0006] The present invention provides the following resin composition for electronic components and semiconductor device. [1] A resin composition for electronic components, comprising an epoxy compound that is liquid at 25°C, a thiol compound that is liquid at 25°C, and a curing agent, and having a glass transition temperature of 80°C or higher after heating at 80°C for 1 hour. [2] The resin composition for electronic components according to [1], wherein the epoxy compound contains four or more epoxy groups in the molecule, and the thiol compound contains four or more thiol groups in the molecule. [3] The resin composition for electronic components according to [1] or [2], which has a viscosity measured at 25°C with an E-type viscometer of 0.01 Pa·s or more and 10 Pa·s or less. [4] The resin composition for electronic components according to any one of [1] to [3], wherein the epoxy compound contains an aromatic ring in the molecule, and has a viscosity of 0.01 Pa s or more and 1000 Pa s or less as measured at 25°C with an E-type viscometer. [5] The resin composition for electronic components according to any one of [1] to [4], wherein the viscosity of the thiol compound measured at 25°C with an E-type viscometer is 0.01 Pa·s or more and 10 Pa·s or less. [6] A semiconductor device comprising: a circuit board; a semiconductor element disposed on the circuit board and electrically connected to the circuit board; and an underfill material disposed between the circuit board and the semiconductor element, wherein the underfill material is a cured product of the resin composition for electronic components according to any one of [1] to [5]. [Effects of the Invention]

[0007] According to the resin composition for electronic parts of the present invention, highly reliable electronic parts can be produced at relatively low temperatures. DETAILED DESCRIPTION OF THE INVENTION

[0008] 1. Resin compositions for electronic components The resin composition for electronic components of the present invention (hereinafter also simply referred to as "resin composition") is a composition useful for manufacturing electronic components, particularly for manufacturing semiconductor devices. The resin composition can be used as an adhesive between a semiconductor element and a substrate of a semiconductor device, a composition for an underfill material that fills the gap between a semiconductor element and a circuit board, or a composition for an encapsulant that encapsulates a semiconductor element. However, the uses of the resin composition for electronic components are not limited to these.

[0009] The resin composition of the present invention contains an epoxy compound that is liquid at 25°C, a thiol compound that is liquid at 25°C, and a curing agent, and has a glass transition temperature of 80°C or higher after heating at 80°C for 1 hour. This resin composition can form a cured product with high heat resistance at a relatively low heating temperature. In other words, this resin composition can be used to form, for example, underfill materials for semiconductor devices at relatively low temperatures, and is less likely to damage other components when forming the underfill material. Meanwhile, the cured product obtained from this resin composition has a sufficiently high glass transition temperature, making it less susceptible to thermal damage, for example, when forming other components of a semiconductor device. Therefore, this resin composition can be used to produce highly reliable electronic components.

[0010] Here, the resin composition of the present invention may contain an epoxy compound, a thiol compound, and a curing agent, but may further contain a stabilizer, various additives, etc. Each component and the physical properties of the resin composition will be described below.

[0011] (epoxy compounds) The epoxy compound may be any compound that is liquid at 25°C and has one or more epoxy groups in its molecule. Preferably, the number of epoxy groups in one molecule is four or more (tetrafunctional), and more preferably four. Tetrafunctional or more epoxy compounds have very high reactivity with the thiol compound described below and are likely to form a dense crosslinked structure. Therefore, the glass transition temperature of the cured product of the resin composition is likely to be further increased. The resin composition may contain only one type of epoxy compound, or two or more types. However, the total amount of tetrafunctional or more epoxy compounds relative to the total amount of epoxy compounds is preferably 50% by mass or more, more preferably 60% by mass or more. When the proportion of tetrafunctional or more epoxy compounds is 75% by mass or more, the glass transition temperature of the cured product of the resin composition is likely to be further increased.

[0012] Furthermore, the viscosity of the epoxy compound measured at 25°C using an E-type viscometer is preferably 0.01 Pa·s or more and 1000 Pa·s or less. The viscosity is more preferably 500 Pa·s or less, and even more preferably 300 Pa·s or less. When the resin composition contains multiple epoxy compounds, it is preferable that the viscosity of each epoxy compound be within the above range. When the viscosity of the epoxy compounds is within the above range, the viscosity of the resin composition is likely to fall within the desired range.

[0013] Here, the epoxy compound may have any of an aromatic ring, an alicyclic structure, and an aliphatic chain structure, but it is more preferable that the epoxy compound has an aromatic ring, since this tends to increase the hardness of the cured product of the resin composition.

[0014] Examples of tetrafunctional or higher aromatic epoxy compounds include compounds in which glycidylamine is bonded to one or more aromatic rings (hereinafter also referred to as "glycidylamine-containing epoxy compounds"). Specific examples of glycidylamine-containing epoxy compounds include tetraglycidyldiaminodiphenylmethane and tetraglycidyl-p-aminophenol, with tetraglycidyldiaminodiphenylmethane being preferred in terms of versatility. The epoxy compounds may be commercially available, including Sumiepoxy ELM-434, Sumiepoxy ELM-434L, and Sumiepoxy ELM-434VL (all manufactured by Sumitomo Chemical Co., Ltd.), Araldite MY720, MY721, and MY0510 (all manufactured by Huntsman Japan), jER604 (manufactured by Mitsubishi Chemical Corporation), and YH-404 (manufactured by Nippon Steel Chemical & Material Co., Ltd.). Examples of aromatic ring-containing epoxy compounds with tetrafunctionality or higher include epoxidation products of 2,2'-diallylbisphenol A diallyl ether with hydrogen peroxide (for example, BATG, manufactured by Resonac).

[0015] The amount of the epoxy compound in the resin composition (the total amount when multiple epoxy compounds are included) is preferably 40% by mass to 60% by mass, more preferably 45% by mass to 55% by mass. When the amount of the epoxy compound in the resin composition is within this range, the glass transition temperature of the cured product of the resin composition is more likely to fall within the desired range.

[0016] (Thiol compounds) The thiol compound may be any compound that is liquid at 25°C and has one or more thiol groups in its molecule. Preferably, the thiol compound has four or more (tetrafunctional) thiol groups in one molecule, and more preferably four. When the thiol compound is tetrafunctional or more, it is likely to form a dense crosslinked structure with the epoxy compound, and the glass transition temperature of the cured resin composition is likely to be further increased. The resin composition may contain two or more types of thiol compounds, but the total amount of tetrafunctional or more thiol compounds relative to the total amount of thiol compounds is preferably 70% by mass or more, more preferably 80% by mass or more. When the proportion of tetrafunctional or more thiol compounds is 90% by mass or more, the glass transition temperature of the cured resin composition is likely to be further increased.

[0017] Furthermore, the viscosity of the thiol compound measured at 25°C with an E-type viscometer is preferably 0.01 Pa·s or more and 10 Pa·s or less. When the resin composition contains multiple thiol compounds, it is preferable that the viscosity of each thiol compound be within this range. When the viscosity of the thiol compounds is within this range, the viscosity of the resin composition is likely to fall within the desired range.

[0018] Here, the thiol compound may be a primary thiol compound or a secondary thiol compound. Examples of tetrafunctional or higher primary thiols include tetrafunctional thiol compounds such as pentaerythritol tetramercaptoacetate, pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tetrakis(4-mercaptobutyrate); and pentafunctional or higher thiol compounds such as dipentaerythritol hexamercaptoacetate, dipentaerythritol hexakis(3-mercaptopropionate), and dipentaerythritol hexakis(4-mercaptobutyrate).

[0019] Examples of tetrafunctional or higher secondary thiol compounds include tetrafunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptopropionate), pentaerythritol tetrakis(4-mercaptovalerate), pentaerythritol tetrakis(3-mercaptovalerate), and pentaerythritol tetrakis(3-mercapto-3-phenylpropionate); and polyfunctional thiol compounds having five or more functional groups such as dipentaerythritol hexakis(3-mercaptobutyrate), dipentaerythritol hexakis(2-mercaptopropionate), dipentaerythritol hexakis(4-mercaptovalerate), dipentaerythritol hexakis(3-mercaptovalerate), and dipentaerythritol hexakis(3-mercapto-3-phenylpropionate).

[0020] Among the above thiol compounds, pentaerythritol tetrakis(3-mercaptopropionate) is preferred from the viewpoints of reactivity and versatility.

[0021] The amount of thiol compound in the resin composition (total amount when multiple epoxy compounds are included) is preferably 40% by mass to 60% by mass, more preferably 45% by mass to 55% by mass. Furthermore, when the total amount (number of moles) of epoxy groups derived from the epoxy compounds present in the resin composition is taken as 1, the amount (number of moles) of thiol groups derived from the thiol compound present in the resin composition is preferably 0.7 to 1.6 equivalents, more preferably 0.9 to 1.2 equivalents. When the content ratio of epoxy groups to thiol groups in the resin composition is within this range, the epoxy groups and thiol groups tend to react efficiently.

[0022] (hardening agent) The curing agent contained in the resin composition is not particularly limited, but is preferably a latent thermosetting agent that does not cure the resin composition at temperatures below 50° C. but can cure the resin composition at temperatures of 80° C. or higher. Examples of the latent thermosetting agent include known curing agents with a melting point of 50° C. or higher and 250° C. or lower (preferably 50° C. or higher and 150° C. or lower) and microcapsule-type curing agents in which various curing components are encapsulated in microcapsules, and it is preferable to include at least a microcapsule-type curing agent.

[0023] The microcapsule-type curing agent may contain microcapsules and a curing component contained in the microcapsules. Examples of the curing component include imidazole compounds, amine compounds, amine adducts, etc. The curing agent may contain only one type of curing component, or two or more types.

[0024] Examples of imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 4-formylimidazole, 2-butyl-4-formylimidazole, dazole, 2-butyl-4-hydroxymethylimidazole, 2-butyl-4-chloro-5-formylimidazole, 2-hydroxymethylimidazole, 1-(2-hydroxyethyl)-imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 2-hydroxymethyl-1-benzylimidazole, 4-hydroxymethyl-2-methylimidazole, 4-formyl-1-methylimidazole, 5-formyl-1-methylimidazole, 4-formyl-5-methylimidazole, 4-formyl-1-tritylimidazole, 4-Carboxymethylimidazole, 4-carboxyethylimidazole, 4-carboxylic acid imidazole, 2-aminoimidazole sulfate, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-formylimidazole, 1-benzyl-5-hydroxymethylimidazole, 1-benzyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethylimidazole, 4-methylimidazole, 1 -cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, and the like.

[0025] Examples of the amine compound include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propanediamine, tetramethyleneamine, 1,5-diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, 1,2-diaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentane, cyclohexylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, aminoethylpiperazine, diethylaminopropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperazine, and the like.

[0026] An amine adduct is an addition compound obtained by reacting a compound having an amine structure with any compound. Examples of the amine adduct include addition compounds obtained by reacting the above-mentioned imidazole compounds or amine compounds with carboxylic acid compounds, sulfonic acid compounds, epoxy resins, etc. (for example, epoxy resins obtained by glycidylating bisphenol F, resins obtained by glycidylating bisphenol A, etc.).

[0027] On the other hand, the capsules encapsulating the curing component are not particularly limited in structure or material as long as they rupture or expand when heated and the curing component can come into contact with the above-mentioned epoxy compound, but it is preferable that the capsules be epoxy resins, as this makes it easier to exhibit the above-mentioned performance.

[0028] Here, the average particle size of the microcapsule-type curing agent is not particularly limited, but is preferably, for example, more than 0.3 μm and not more than 13 μm, and more preferably 1 μm or more and not more than 11 μm. Furthermore, the curing component encapsulated in the capsules is preferably solid, and its average particle size is preferably more than 0.25 μm and not more than 12 μm, and more preferably more than 1 μm and not more than 10 μm. When the average particle size of the curing component or the average particle size of the microcapsule-type curing agent encapsulating the curing component is within the above range, the curing component is more likely to perform its function uniformly in the resin composition when heated. The above average particle size is the Stokes diameter measured by laser diffraction / light scattering.

[0029] The microcapsule-type curing agent can be produced by a known method. For example, a curing component having a desired average particle size may be prepared, dispersed in a dispersion medium together with capsule components, and the capsule components may be precipitated on the surface of the curing component. Alternatively, a solution may be prepared by dissolving capsule raw materials in a solvent, and the curing component may be added to the solution, and the capsule raw materials may be reacted on the surface of the curing component to form capsules.

[0030] The microcapsule-type curing agent, in which the curing component is encapsulated in microcapsules, may be a commercially available product. Examples of commercially available products include Novacure (registered trademark) HX-3742, HX-3722, HXA-3922HP, HXA-4922HP, and HXA-4922HP (all manufactured by Asahi Kasei Corporation). Note that the commercially available products are distributed in a state in which the microcapsule-type curing agent is dispersed in an epoxy compound (e.g., bisphenol A epoxy resin).

[0031] When the curing agent is the microcapsule-type curing agent, the amount of the curing component in the resin composition is preferably 0.1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 30% by mass or less, relative to the total amount of the resin composition. When the amount of the curing component of the microcapsule-type curing agent in the resin composition is within this range, the curability of the resin composition can be further improved.

[0032] (stabilizer) The resin composition may further contain a stabilizer to enhance the stability of the resin composition. Examples of stabilizers include compounds that enhance the stability of the above-mentioned epoxy compounds (especially amines). Examples of such stabilizers include boron-based compounds, phosphoric acid, alkyl phosphate esters, p-toluenesulfonic acid, and methyl p-toluenesulfonate. Examples of boron-based compounds include trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tris(2-ethylhexyloxy)borane, triphenylborate, and various borate esters. Examples of the alkyl phosphate esters include trimethyl phosphate and tributyl phosphate. The resin composition may contain only one stabilizer, or two or more stabilizers.

[0033] The amount of the stabilizer is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.05% by mass or more and 25% by mass or less, relative to the total amount of the resin composition. When the amount of the stabilizer is within this range, the stability of the resin composition is likely to be further improved.

[0034] (Other ingredients) The resin composition may further contain components other than those described above, as long as the objects and effects of the present invention are not impaired. Examples of the components other than those described above include fillers, modifiers, various additives, etc.

[0035] Examples of the filler include glass beads, styrene-based polymer particles, methacrylate-based polymer particles, ethylene-based polymer particles, propylene-based polymer particles, etc. The resin composition may contain only one type of filler, or may contain two or more types of fillers.

[0036] Specific examples of the modifier include a polymerization initiator, an antioxidant, a leveling agent, a wettability improver, a surfactant, a plasticizer, a solvent, a silane coupling agent, etc. The resin composition may contain only one of these modifiers, or may contain two or more of them.

[0037] Specific examples of the additives include an ultraviolet absorber, an antiseptic, an antibacterial agent, etc. The resin composition may contain only one of these, or may contain two or more of them.

[0038] However, the amount of the other components is more preferably 0.01% by mass or more and 10% by mass or less relative to the total amount of the resin composition.

[0039] (Physical properties of resin composition and its cured product) The preferred viscosity of the resin composition of the present invention is selected appropriately depending on the application, but when the resin composition is used as an underfill material for a semiconductor device, the viscosity measured with an E-type viscometer at 25°C is preferably 0.01 Pa·s or more and 10 Pa·s or less, and more preferably 0.1 Pa·s or more and 5 Pa·s or less. When the viscosity of the resin composition is within this range, the resin composition can easily penetrate into the gaps between the semiconductor element and the circuit board in the semiconductor device by capillary action, making it easier to fill these gaps.

[0040] Furthermore, the chloride ion content of the resin composition is preferably 1200 ppm or less, more preferably 900 ppm or less. If the chloride ion concentration in the cured resin composition is high, chloride ions may migrate from the cured product, causing corrosion of metals in electronic components. In contrast, if the chloride ion content in the resin composition is 900 ppm or less, the chloride ion concentration in the cured product can be reduced, making it easier to obtain stable electronic components over a long period of time. The chloride ion concentration in the resin composition was measured by placing the resin composition in a pressure-resistant container made of polytetrafluoroethylene (PTFE), weighing it, adding 10 mL of pure water, and sealing it. The chlorine was then extracted by heating in an oven at 100°C (set temperature) for 20 hours. After cooling to room temperature, the extract was collected and quantitatively analyzed for chloride ions using ion chromatography (1C method).

[0041] The resin composition has a glass transition temperature (Tg) of 80°C or higher, preferably 90°C or higher and 200°C or lower, and more preferably 100°C or higher and 180°C or lower, after heating at 80°C for 1 hour. If the resin composition has a glass transition temperature of 80°C or higher after heating at 80°C for 1 hour, the cured resin composition is less likely to melt or soften and can retain its shape even when heat is applied during the production of electronic components. Note that the glass transition temperature in this specification is a value determined as follows using a viscoelasticity measuring device (DMS). Specifically, it is a value determined by the following method. First, the resin composition is applied with an applicator to a thickness of 100 μm. Then, the applied resin composition is heated in an oven at 80°C for 1 hour to obtain a cured film having a thickness of 100 μm. The cured film is cut into strips and heated from room temperature to 180°C at a rate of 5°C / min using a viscoelasticity measuring device (DMS). The point at which the ratio of the storage modulus (E') to the loss modulus (E'') is maximum is taken as the glass transition temperature.

[0042] (Method of producing resin composition) The resin composition can be prepared by mixing an epoxy compound, a thiol compound, a curing agent, a stabilizer, and other components as needed. The order of mixing the components is not particularly limited; all components may be mixed at once, or specific components may be mixed first, followed by the remaining components. For example, the curing agent may be mixed later. The mixing method is not particularly limited; mixing can be performed by a known method, such as a triple-roll mill.

[0043] 2. Semiconductor Devices The above-mentioned resin composition can be used, for example, as a material for forming an underfill material for a semiconductor device. For example, the resin composition can be used as a material for forming an underfill material for a semiconductor device having a circuit board, a semiconductor element disposed on the circuit board and electrically connected to the circuit board, and an underfill material disposed between the circuit board and the semiconductor element.

[0044] The circuit board and semiconductor element in the semiconductor device can be any known circuit board or semiconductor element. The circuit board and semiconductor element may be electrically connected, for example, by solder balls. The method for forming the underfill material using the resin composition is not particularly limited. For example, the underfill material can be formed by joining the circuit board and the semiconductor element with solder or the like, filling the gap between them with the resin composition, and then curing the gap. Because the gap is very narrow, it is preferable to fill the resin composition using capillary action. The resin composition is preferably cured by heating at 80°C to 120°C for approximately 60 minutes. [Example]

[0045] The present invention will be described below with reference to examples, which should not be construed as limiting the scope of the present invention.

[0046] [material] In the examples and comparative examples, the following materials were used.

[0047] [Epoxy Compound] YH-404: Tetraglycidyldiaminodiphenylmethane (tetrafunctional) (YH-404 manufactured by Nippon Steel Chemical & Material Co., Ltd., liquid at 25°C) YL983U: Bisphenol F type epoxy resin (bifunctional) (YL983U, manufactured by Mitsubishi Chemical Corporation, liquid at 25°C) YL980: Bisphenol A epoxy resin (bifunctional) (YL980, manufactured by Mitsubishi Chemical Corporation, liquid at 25°C) Tepic-VL: 1,3,5-tris(4,5-epoxypentyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trifunctional) (Tepic-VL, manufactured by Nissan Chemical Industries, Ltd., liquid at 25°C)

[0048] [Thiol compounds] PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) (tetrafunctional) (SC Organic Chemicals, liquid at 25°C) TMMP: Trimethylolpropane tris(3-mercaptopropionate) (trifunctional) (manufactured by SC Organic Chemicals, liquid at 25°C)

[0049] [Curing agent] HXA-4922HP: Microencapsulated imidazole curing agent (dispersion medium: epoxy resin, curing component amount: 30-40% by mass, Novacure (registered trademark) HXA-4922HP, manufactured by Asahi Kasei Corporation) 2MA-OK: Imidazole-based curing agent (2MA-OK, manufactured by Shikoku Chemicals Co., Ltd.)

[0050] [Stabilizer] L-07N: Boric acid ester compound (L-07N, manufactured by Shikoku Chemicals Co., Ltd.)

[0051] [Examples 1 to 3, Comparative Examples 1 to 5] An epoxy compound, a thiol compound, a curing agent, and a stabilizer were added to a flask in the mass ratios shown in Table 1, and the mixture was stirred at room temperature to obtain a resin composition.

[0052] [evaluation] The viscosity of the resin compositions prepared in the examples and comparative examples, the Tg after heating at 80°C for 1 hour, the curability of the resin compositions after heating at 80°C for 1 hour, and the storage modulus at 100°C were evaluated by the following methods.

[0053] ·viscosity Within half a day after preparation, the viscosity of the resin composition was measured at 25°C using an E-type viscometer (Toki Sangyo E-type viscometer TV-200, using a 3° cone). The results are shown in Table 1. The viscosities of the epoxy compound and thiol compound used in preparing the resin composition were also measured in the same manner.

[0054] Tg after heating at 80℃ for 1 hour The resin composition was applied to a thickness of 100 μm using an applicator. It was then heated in an oven at 80°C for 1 hour to obtain a cured film with a thickness of 100 μm. The cured film was cut into strips and heated from room temperature to 180°C at a rate of 5°C / min using a viscoelasticity measuring device (DMS). The point at which the ratio of the storage modulus (E') to the loss modulus (E'') was maximized was taken as the glass transition temperature. The results are shown in Table 1.

[0055] Hardening after heating at 80℃ for 1 hour The resin composition was applied to a thickness of 100 μm using an applicator. It was then heated in an oven at 80°C for 1 hour to obtain a cured film with a thickness of 100 μm. The tackiness of the film was then checked. If there was no tackiness, it was judged to be cured, and if there was tackiness, it was judged to be uncured. The results are shown in Table 1.

[0056] Storage modulus at 100℃ after heating at 80℃ for 1 hour A 100 μm cured film obtained by the same method as above (heated at 80°C for 1 hour) was measured using a viscoelasticity measuring device (DMS). The temperature was raised from room temperature to 180°C at a rate of 5°C / min, and the storage modulus (E') at 100°C was evaluated as follows. ○: Storage modulus is 100 MPa or more but less than 3 GPa ×: Storage modulus is 1 MPa or more and less than 100 MPa

[0057] [Table 1]

[0058] As shown in Table 1 above, resin compositions containing an epoxy compound that is liquid at 25°C, a thiol compound that is liquid at 25°C, and a curing agent, and having a Tg of 80°C or higher after heating at 80°C for 1 hour, could be cured without heating to a high temperature. Furthermore, these cured products had a storage modulus of 100 MPa or higher at 100°C, and could maintain adhesive strength even at high temperatures. Therefore, it can be said that highly reliable electronic components can be produced using these resin compositions for electronic components (Examples 1 to 3).

[0059] In contrast, even if a composition contained an epoxy compound that is liquid at 25°C, a thiol compound that is liquid at 25°C, and a curing agent, it may not be able to cure (Comparative Examples 4 and 5). Even if the composition could be cured by heating at 80°C for 1 hour, if its Tg was low, the storage modulus at high temperatures was low and the heat resistance was insufficient (Comparative Examples 1 to 3). [Industrial Applicability]

[0060] The resin composition for electronic parts of the present invention makes it possible to produce highly reliable electronic parts at relatively low temperatures, and is therefore extremely useful in the field of producing various electronic parts.

Claims

1. The composition contains an epoxy compound that is liquid at 25°C, a thiol compound that is liquid at 25°C, and a curing agent, The glass transition temperature after heating at 80°C for 1 hour is 80°C or higher. Resin composition for electronic parts.

2. the epoxy compound contains four or more epoxy groups in the molecule, The thiol compound contains four or more thiol groups in the molecule. The resin composition for electronic parts according to claim 1.

3. The viscosity measured at 25°C using an E-type viscometer is 0.01 Pa s or more and 10 Pa s or less. The resin composition for electronic parts according to claim 1.

4. the epoxy compound contains an aromatic ring in the molecule, the viscosity of the epoxy compound measured at 25°C with an E-type viscometer is 0.01 Pa s or more and 1000 Pa s or less; The resin composition for electronic parts according to claim 1.

5. the viscosity of the thiol compound measured at 25°C with an E-type viscometer is 0.01 Pa s or more and 10 Pa s or less; The resin composition for electronic parts according to claim 1.

6. A circuit board; a semiconductor element disposed on the circuit board and electrically connected to the circuit board; an underfill material disposed between the circuit board and the semiconductor element; and The underfill material is a cured product of the resin composition for electronic components according to any one of claims 1 to 5. Semiconductor device.

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