Epoxy resin composition, adhesive agent, sealing material, cured article, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing: an epoxy resin composition with which it is possible to suppress the discoloration of an object having the composition applied thereto even when the composition contains a specific trithiol compound; an adhesive agent or a sealing material containing the composition; a cured article; and a semiconductor device or an electronic component.　Provided are: an epoxy resin composition containing (A) an epoxy resin having a halogen content of 1600 ppm or less, (B) a thiol compound represented by chemical formula (I), and (C) a basic curing catalyst; an adhesive agent or a sealing material containing the epoxy resin composition; a cured article; and a semiconductor device or an electronic component.

Description

Epoxy resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components

[0001] The present invention relates to an epoxy resin composition, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.

[0002] Currently, adhesives, sealants, etc. containing curable resin compositions, particularly epoxy resin compositions, are often used in the assembly and mounting of semiconductor devices and electronic components, such as semiconductor chips, for the purpose of maintaining reliability, etc. Compounds containing multiple thiol groups in the molecule are well known to be useful as curing agents for epoxy resins. For example, epoxy resin compositions are known that use a polythiol compound as a curing agent and contain a reaction product of an amine and an epoxy compound as a curing accelerator (e.g., Patent Documents 1 and 2).

[0003] Patent Document 3 discloses a compound having the following structural formula: Disclosed is a trithiol compound having the formula:

[0004] JP 6-211969 JP 6-211970 JP 2022-180364

[0005] Patent Document 3 discloses that when a resin composition containing this trithiol compound is used as an adhesive, it is possible to improve the adhesive strength with an adherend, which has been a conventional problem. The present inventors found that when an epoxy resin composition containing this trithiol compound was applied to a metal substrate, significant discoloration of the metal substrate was observed in a moisture resistance reliability test, compared to epoxy resin compositions containing other conventional thiol compounds. Discoloration not only reduces commercial value due to poor appearance, but can also lead to corrosion, and once corrosion products are generated, they can spread to surrounding metals, which can be particularly problematic in semiconductor devices and electronic components where the distance between components is short.

[0006] An object of the present invention is to provide an epoxy resin composition that suppresses discoloration of an adherend to which it is applied, even when it contains a specific trithiol compound, an adhesive or sealant containing the same, a cured product, and a semiconductor device or electronic component.

[0007] Specific means for solving the above problems are as follows: Embodiments of the present invention include an epoxy resin composition, an adhesive or sealant, a cured product, and a semiconductor device or electronic component having the following aspects: (1) (A) an epoxy resin having a halogen content of 1600 ppm or less, (B) a compound represented by the chemical formula (I): and (C) a basic curing catalyst. (2) The epoxy resin composition according to Aspect (1) above, wherein the basic curing catalyst (C) is a thermally latent curing catalyst. (3) The epoxy resin composition according to Aspect (1) or (2) above, wherein the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of component (A)] / [number of thiol group equivalents of component (B)]) is 0.1 to 10. (4) The epoxy resin composition according to any one of Aspects (1) to (3) above, wherein components (A) to (C) are contained in a single container. (5) The epoxy resin composition according to any one of Aspects (1) to (3) above, wherein components (A) to (C) are divided into two or more containers. (6) An adhesive or sealant comprising the epoxy resin composition according to any one of Aspects (1) to (5). (7) The adhesive or sealant according to the above aspect (6), which is for use in a semiconductor device or an electronic component. (8) A cured product obtained by curing the epoxy resin composition according to any one of the above aspects (1) to (5), or the adhesive or sealant according to the above aspect (6) or (7). (9) A semiconductor device or an electronic component comprising the cured product according to the above aspect (8).

[0008] According to an embodiment of the present invention, there are provided an epoxy resin composition that suppresses discoloration of an adherend to which it is applied, even when it contains a specific trithiol compound, an adhesive or sealant containing the same, a cured product obtained by curing the composition or the like, and a semiconductor device or electronic component containing the cured product.

[0009] 1 is a photograph taken from above of a copper substrate used in the discoloration evaluation of Example 1, Comparative Example 2, and Reference Example 1 after being left standing in an 85° C. / 85% RH environment for 20 hours.

[0010] In this specification, following the convention in the field of synthetic resins, a name including the term "resin," which normally refers to a polymer (particularly a synthetic polymer), may be used for a component constituting a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing.

[0011] [Epoxy Resin Composition] An epoxy resin composition according to one embodiment of the present invention comprises: (A) an epoxy resin having a halogen content of 1600 ppm or less; (B) a compound represented by the chemical formula (I): and (C) a basic curing catalyst. According to this embodiment, it is possible to provide an epoxy resin composition that suppresses discoloration of an adherend to which it is applied, even when it contains a thiol compound represented by chemical formula (I).

[0012]

[0033] (A) Epoxy Resin Having a Halogen Content of 1600 ppm or Less

[0034] The epoxy resin composition of this embodiment contains (A) an epoxy resin having a halogen content of 1600 ppm or less (hereinafter also referred to as "component (A)"). By including (A) an epoxy resin having a halogen content of 1600 ppm or less as the main component, it is possible to provide an epoxy resin composition that suppresses discoloration of an adherend to which it is applied, even when the epoxy resin contains a thiol compound represented by chemical formula (I) as a curing agent for the epoxy resin.

[0013] The present inventors have found that, although epoxy resin compositions containing a thiol compound represented by chemical formula (I) have excellent adhesive strength, when this epoxy resin composition is applied to a metal substrate, significant discoloration of the metal substrate is observed in a humidity-resistance reliability test compared to epoxy resin compositions containing other conventional thiol compounds. The reason for this discoloration is unclear, but the present inventors speculate as follows: First, the thiol compound represented by chemical formula (I) has significantly fewer polar moieties other than thiol groups in its structure than other conventional thiol compounds. Therefore, when it comes into contact with a highly polar surface, such as a metal surface, the thiol groups are relatively easily accessible to the metal surface. Therefore, when the epoxy resin composition is applied to a metal substrate, the thiol groups of the thiol compound represented by chemical formula (I) are more likely to be present on the metal surface than those of other conventional thiol compounds. It is believed that during the humidity-resistance reliability test, halogens and water, which have a high affinity for polar metal surfaces, migrate to the metal surface, causing some kind of reaction between the thiol groups on the metal surface, the halogens, water, and the metal, resulting in the discoloration. Therefore, in order to reduce the halogen concentration on the metal surface, the halogen content of the epoxy resin contained in the resin composition was controlled to a certain amount or less, and it was found that discoloration of the metal substrate was suppressed.

[0014] The halogen content of the epoxy resin as component (A) is 1600 ppm or less, preferably 1500 ppm. The halogen is at least one selected from fluorine, chlorine, bromine, and iodine. Chlorine may be contained in the epoxy resin during the synthesis process. In one embodiment, the chlorine content of the epoxy resin as component (A) is 1600 ppm or less, preferably 1500 ppm. In this specification, the halogen content of the epoxy resin, for example, when the halogen is chlorine, refers to the total chlorine content, which can be quantified by known methods, such as sample combustion-ion chromatography in accordance with BS EN 14582:2007. The principle of this method is to introduce oxygen or argon into a heated quartz combustion tube to combust the sample, absorb the generated combustion gas into an absorption liquid, and fractionate and quantify this absorption liquid using ion chromatography to determine the content in the sample. Examples of this pretreatment method include the flask combustion method, bomb combustion method, and combustion tube method.

[0015] The epoxy resin used as component (A) is not particularly limited as long as it has a halogen content of 1600 ppm or less and at least two epoxy groups. The term "epoxy resin" is a general term for thermosetting resins that can be cured by forming a crosslinked network with the epoxy groups present in the molecule, and includes prepolymer compounds before curing. Considering the need to ensure heat resistance, epoxy resins with two to six epoxy groups are more preferred, and those with two epoxy groups are even more preferred. The epoxy resin may be liquid or solid at 25°C, but is preferably liquid at 25°C. Epoxy resins are broadly classified into aromatic epoxy resins and epoxy resins without aromatic rings.

[0016] Aromatic epoxy resins are epoxy resins that have a structure containing an aromatic ring such as a benzene ring. Many of the epoxy resins that have been commonly used so far, such as bisphenol A epoxy resins, are of this type. Examples of aromatic epoxy resins include, but are not limited to, bisphenol A-type epoxy resins; branched polyfunctional bisphenol A-type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F-type epoxy resins; novolac-type epoxy resins; tetrabromobisphenol A-type epoxy resins; fluorene-type epoxy resins; biphenylaralkyl-type epoxy resins; diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; biphenyl-type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidylamine-type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and naphthalene ring-containing epoxy resins. These may be used alone or in combination of two or more. Preferred aromatic epoxy resins are bisphenol F epoxy resins, bisphenol A epoxy resins, and glycidylamine epoxy resins, with those having an epoxy equivalent of 90 to 500 g / eq being more preferred, and those having an epoxy equivalent of 90 to 400 g / eq being even more preferred. The aromatic epoxy resin may be oxyalkylene-modified, such as EO (ethylene oxide)-modified or PO (propylene oxide)-modified. The aromatic epoxy resin is preferably liquid at 25°C. The viscosity at 25°C is preferably 0.1 to 100 Pa·s, more preferably 0.5 to 100 Pa·s, and particularly preferably 1 to 100 Pa·s.

[0017] In this specification, unless otherwise specified, viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833. Specifically, viscosity can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular limitations on the equipment, rotor, or measurement range used.

[0018] Epoxy resins without an aromatic ring include, for example, aliphatic epoxy resins and epoxy resins with a heterocycle.

[0019] Examples of aliphatic epoxy resins include: diepoxy compounds such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, and dicyclopentadiene diglycidyl ether; triepoxy compounds such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; alicyclic epoxy resins such as vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; Examples of suitable aliphatic epoxy resins include, but are not limited to, hydrogenated bisphenol A diepoxy resins such as hydrogenated bisphenol A diglycidyl ether; glycidylamine epoxy resins such as tetraglycidyl bis(aminomethyl)cyclohexane; hydantoin epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and silicone-backbone epoxy resins such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane. The aliphatic epoxy resin preferably has an epoxy equivalent of 90 to 450 g / eq. It is also preferably liquid at 25°C. It is also preferably one with a viscosity at 25°C of 10 to 10,000 mPa·s, more preferably 10 to 5,000 mPa·s.

[0020] Examples of epoxy resins having a heterocycle include isocyanuric acid-type epoxy resins and glycoluril-type epoxy resins. The epoxy resin having a heterocycle preferably has an epoxy equivalent of 80 to 450 g / eq. From the viewpoint of workability, it is preferable that the resin be liquid at 25°C. It is also preferable that the viscosity at 25°C is 100 to 50,000 mPa·s, and more preferably 100 to 5,000 mPa·s. On the other hand, from the viewpoint of adhesion, it is preferable that the resin be solid at 25°C.

[0021] The epoxy resin (A) may be used alone or in combination of two or more thereof.

[0022] In the present embodiment, the content of the epoxy resin (A) in the epoxy resin composition is preferably 10 to 90% by weight, more preferably 15 to 85% by weight, and even more preferably 20 to 80% by weight, relative to the total weight of the epoxy resin composition.

[0023] In this embodiment, the epoxy resin composition preferably does not contain an epoxy resin having a halogen content exceeding 1600 ppm. In one embodiment, when the epoxy resin composition contains an epoxy resin having a halogen content exceeding 1600 ppm, there may be areas in the epoxy resin composition where the halogen concentration is locally high, which may result in localized discoloration. In applications where the composition is used in a small area, such as adhesives or sealants for semiconductor devices or electronic components, even localized discoloration may lead to corrosion and cause electrical failure. When the epoxy resin composition contains an epoxy resin having a halogen content exceeding 1600 ppm, the amount is, for example, 10 parts by weight or less, preferably 5 parts by weight or less, per 100 parts by weight of the total epoxy resin. Furthermore, the halogen content of the entire epoxy resin is preferably 1600 ppm or less, and more preferably 1500 ppm or less. Furthermore, the halogen content of the entire epoxy resin composition is preferably 1600 ppm or less, and more preferably 1500 ppm or less.

[0024] (B) Thiol Compound Represented by Chemical Formula (I) The epoxy resin composition of the present embodiment comprises (B) a thiol compound represented by chemical formula (I): The thiol compound represented by chemical formula (I) acts as a curing agent for epoxy resins. The thiol compound represented by chemical formula (I) can be synthesized, for example, by reacting 1,2,3-triallyloxypropane with a thiocarboxylic acid and solvolyzing the resulting thioester, according to the method described in Patent Document 3 (JP-A-2022-180364) or the method described in JP-A-2023-126883.

[0025] (B) The thiol compound represented by chemical formula (I) acts as a curing agent for the epoxy resin, and the curing agent may contain by-products produced during the synthesis of the thiol compound represented by chemical formula (I). Examples of by-products include, but are not limited to, the compounds represented by the following chemical formulas (I-1) to (I-9) described in JP 2022-180364 A.

[0026]

[0027]

[0028] Examples of by-products include, for example, thiol compounds represented by the formulas (I-1) to (I-45), (1) multimers of these thiol compounds (e.g., dimers and trimers), (2) condensates of two or more selected from these thiol compounds, and (3) condensates of one or more selected from the thiol compounds represented by the formulas (IV-1) to (IV-6) described in JP-A-2023-126883. However, they are not limited thereto.

[0029] Component (B) contains a by-product of the thiol compound represented by the chemical formula (I), for example, the compounds represented by the chemical formulas (I-1) to (I-9) described in JP-A-2022-180364 and the compounds described in JP-A-2023-126883, the content of the thiol compound represented by the chemical formula (I) to the content of the by-product of the thiol compound represented by the chemical formula (I) is preferably 0.02 to 0.3, more preferably 0.02 to 0.25, even more preferably 0.05 to 0.25, most preferably 0.05 to 0.20. The ratio of the content of each compound in the curing agent is a value calculated using the size of the peak area of ​​each component when the curing agent is analyzed by liquid chromatography.

[0030] In this embodiment, the content of component (B) in the epoxy resin composition is preferably 1 to 70 wt %, more preferably 10 to 60 wt %, and even more preferably 20 to 50 wt %, based on the total weight of the epoxy resin composition. Compared to other conventional thiol compounds, component (B) has significantly fewer polar moieties other than thiol groups in its structure, so when it comes into contact with a highly polar surface such as a metal surface, the thiol groups are relatively easily accessible to the metal surface. Therefore, even when the content of component (B) in the epoxy resin composition is low, discoloration of the metal substrate may occur. In this embodiment, the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of component (A)] / [number of thiol group equivalents of component (B)]) is preferably 0.1 to 10, more preferably 0.2 to 10, 0.3 to 10, 0.4 to 10, or 0.5 to 10.

[0031] In this specification, functional group equivalents such as thiol equivalent and epoxy equivalent represent the molecular weight of a compound per functional group, and functional group equivalents such as thiol group equivalent number and epoxy group equivalent number represent the number of functional groups (equivalent number) per weight (charged amount) of a compound.

[0032] Theoretically, the epoxy equivalent of an epoxy resin is the molecular weight of the epoxy resin divided by the number of epoxy groups in one molecule. The actual epoxy equivalent can be determined by the method described in JIS K7236. The epoxy group equivalent of an epoxy resin is the number of epoxy groups (equivalent number) per weight (charged amount) of epoxy resin, and is the quotient obtained by dividing the weight (g) of the epoxy resin by the epoxy equivalent of that epoxy resin (when multiple epoxy resins are contained, the sum of such quotients for each epoxy resin).

[0033] Theoretically, the thiol equivalent of a thiol compound is the molecular weight of the thiol compound divided by the number of thiol groups in one molecule. The actual thiol equivalent can be determined, for example, by determining the thiol value by potentiometric measurement. This method is widely known and is disclosed, for example, in paragraph

[0079] of JP 2012-153794 A. The thiol group equivalent of a thiol compound is the number of thiol groups (equivalents) per weight (charge amount) of the thiol compound, and is the quotient obtained by dividing the weight (g) of the thiol compound by the thiol equivalent of that thiol compound (when multiple thiol compounds are included, the sum of such quotients for each thiol compound).

[0034] (C) Basic Curing Catalyst The epoxy resin composition of this embodiment contains (C) a basic curing catalyst (hereinafter also referred to as "component (C)"). By using component (C), the epoxy resin composition of this embodiment can be cured in a short time even under low temperature conditions. The basic curing catalyst used in this embodiment is not particularly limited as long as it is a curing catalyst for epoxy resins, and known basic curing catalysts can be used.

[0035] Component (C) is preferably a latent curing catalyst. A latent curing catalyst is a compound that is inactive at room temperature but is activated by heating to function as a curing catalyst. Examples include imidazole compounds that are solid at room temperature; solid-dispersed amine adduct latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts). From the viewpoints of pot life and curability, solid-dispersed amine adduct latent curing catalysts are preferred as component (C).

[0036] Examples of imidazole compounds that are solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Examples of the methylimidazole include, but are not limited to, isocyanuric acid adducts, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0037] Examples of epoxy compounds used as one of the raw materials for producing a solid dispersion type amine adduct latent curing catalyst (amine-epoxy adduct) include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; phthalic acid, terephthalic acid, and the like; Examples of epoxy compounds include, but are not limited to, polyglycidyl esters obtained by reacting a polycarboxylic acid such as carboxylic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, and epoxidized polyolefin; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0038] The amine compound used as another raw material for producing the solid dispersion-type amine adduct latent curing catalyst may be any compound as long as it has one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds include, but are not limited to, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0039] Among these, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing catalysts with excellent curing acceleration capabilities. Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as imidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4 ... 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as thiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0040] Further, examples of the isocyanate compound used as another manufacturing raw material for the solid dispersion type amine adduct latent curing catalyst include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0041] Examples of urea compounds include, but are not limited to, urea and thiourea.

[0042] The solid-dispersed latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned combination of two components: (a) an amine compound and an epoxy compound, (b) a combination of three components: these two components and an active hydrogen compound, or (c) a combination of two or three components: an amine compound and an isocyanate compound and / or a urea compound. These can be easily prepared by mixing the components, reacting them at a temperature from room temperature to 200°C, cooling them to solidify them, and then pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0043] Representative examples of commercially available latent curing catalysts include amine-epoxy adducts (amine adducts), such as "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), "Hardener X-3670S" (product name of ACR Co., Ltd.), "Novacure HX-3742" (product name of Asahi Kasei Corporation), and " Examples of such urea-type adducts include Novacure HX-3721 (product name of Asahi Kasei Corporation), Novacure HXA9322HP (product name of Asahi Kasei Corporation), Novacure HXA3922HP (product name of Asahi Kasei Corporation), Novacure HXA3932HP (product name of Asahi Kasei Corporation), Novacure HXA5945HP (product name of Asahi Kasei Corporation), Novacure HXA5911HP (product name of Asahi Kasei Corporation), and Novacure HXA9382HP (product name of Asahi Kasei Corporation). Examples of the component (C) include, but are not limited to, "Fujicure FXR1020" (T&K TOKA Corporation), "Fujicure FXR-1030" (T&K TOKA Corporation), "Fujicure FXR1121" (T&K TOKA Corporation), "Fujicure FXR1081" (T&K TOKA Corporation), "Fujicure FXR1061" (T&K TOKA Corporation), and "Fujicure FXR1171" (T&K TOKA Corporation). Component (C) may be used singly or in combination of two or more.

[0044] The content of component (C) in the epoxy resin composition is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 1 to 10% by weight, based on the total weight of the resin composition.

[0045] Incidentally, component (C) may be provided in the form of a dispersion in an epoxy resin. When component (C) in such a form is used, it is preferable to calculate the ratio of the number of epoxy group equivalents of the entire epoxy resin to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of the entire epoxy resin] / [number of thiol group equivalents of component (B)]) by combining the number of epoxy equivalents of the epoxy resin in which it is dispersed and the number of epoxy equivalents of component (A). In the present embodiment, the ratio of the number of epoxy group equivalents of the entire epoxy resin to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of the entire epoxy resin] / [number of thiol group equivalents of component (B)]) is preferably 0.1 to 10, more preferably 0.2 to 8, even more preferably 0.3 to 6, particularly preferably 0.4 to 2, and most preferably 0.5 to 1.5.

[0046] In this specification, when component (C) contains an epoxy resin, the halogen content of the epoxy resin is preferably 1600 ppm or less.

[0047] The epoxy resin composition of the present embodiment may contain optional components other than the above components (A) to (C), such as those described below, as needed, if desired.

[0048] Thiol Compound Other Than Component (B) The epoxy resin composition of the present embodiment may contain a thiol compound other than component (B) (hereinafter also referred to as "other thiol compound"). Other thiol compounds include, for example, aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds; mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; Mercaptopropionic acid esters such as pentaerythritol tetrakis(3-mercaptopropionate); epoxy resin terminal mercapto compounds; 3,6-dioxa-1,8-octanedithiol, mercaptoalkyl ether disulfide compounds, mercaptoalkyl ether compounds such as 2,2'-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol, 3,3'-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, and 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol; Glycoluril-type thiols such as 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril;Examples of triazine thiols include 2-{2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl}ethyl 3-sulfanylpropionate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, and tris(3-mercaptopropyl)isocyanurate;

[0049] Other examples of other thiol compounds include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,4 ,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol, 3-[2,3-bis(3-sulfanyl propoxy)propoxy]propane-1-thiol, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)ethyl)methane bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl )-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-Dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianyl thio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercapto 4-[3,4-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane

[0033] 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, etc.

[0050] These other thiol compounds may be used alone or in combination of two or more.

[0051] In this embodiment, the weight ratio of the thiol compound of component (B) to the other thiol compounds in the epoxy resin composition ([thiol compound of component (B)]:[other thiol compounds]) is preferably set to 100:0 to 1:99. Component (B) has significantly fewer polar moieties other than thiol groups in its structure than other conventional thiol compounds, and therefore, when it comes into contact with a highly polar surface such as a metal surface, the thiol groups are relatively likely to approach the metal surface. Therefore, even when the content of component (B) in the epoxy resin composition is low, discoloration of the metal substrate may occur.

[0052] When a thiol compound other than component (B) is contained, it is preferable to add the thiol equivalent number of component (B) and the thiol equivalent number of the thiol compound other than component (B) to calculate the ratio of the epoxy group equivalent number of the whole epoxy resin to the thiol group equivalent number of the whole thiol compounds ([epoxy group equivalent number of whole epoxy resin] / [thiol group equivalent number of whole thiol compounds]). In the present embodiment, the ratio of the epoxy group equivalent number of the whole epoxy resin to the thiol group equivalent number of the whole thiol compounds ([epoxy group equivalent number of whole epoxy resin] / [thiol group equivalent number of whole thiol compounds]) is preferably 0.1 to 10, more preferably 0.2 to 8, even more preferably 0.3 to 6, particularly preferably 0.4 to 2, and most preferably 0.5 to 1.5.

[0053] Filler The epoxy resin composition of this embodiment may contain a filler to the extent that the effects of the present invention are not impaired. By containing a filler in the epoxy resin composition, the linear expansion coefficient of the cured product obtained by curing the epoxy resin composition can be reduced, and thermal cycle resistance can be improved. Furthermore, if the filler has a low elastic modulus, stress generated in the cured product can be alleviated, and long-term reliability can be improved. Fillers are broadly classified into inorganic fillers and organic fillers.

[0054] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. One or more inorganic fillers may be used, or two or more may be used in combination. As the inorganic filler, silica filler is preferably used because it allows for a high loading. Amorphous silica is preferred as the silica. The surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0055] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, filler having a urethane skeleton, filler having a butadiene skeleton, styrene filler, etc. The organic filler may be surface-treated.

[0056] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0057] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d ５０ ) By setting the average particle size of the filler to the upper limit or less, sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, which can prevent wear on the jet dispenser nozzle and scattering of the resin composition ejected from the jet dispenser nozzle outside the desired area. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. In one aspect of this embodiment, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 μm or more but less than 0.1 μm may be used in combination with a filler having an average particle size of 0.1 μm to 6.0 μm.

[0058] The content of the filler in the epoxy resin composition of the present embodiment is preferably 15 to 50 wt %, more preferably 20 to 45 wt %, and even more preferably 20 to 40 wt %, relative to the total weight of the epoxy resin composition.

[0059] Stabilizer The epoxy resin composition of this embodiment may contain a stabilizer, if desired, within a range that does not impair the effects of the present invention. The stabilizer can improve the storage stability of the epoxy resin composition of this embodiment and extend its pot life. Various known stabilizers can be used as the stabilizer, but at least one selected from the group consisting of liquid borate ester compounds, aluminum chelates, and organic acids is preferred because of its high effect of improving storage stability.

[0060] Examples of liquid boric acid ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate. Liquid borate ester compounds are preferred because they are liquid at room temperature (25°C), and therefore can keep the viscosity of the epoxy resin composition low. As the aluminum chelate, for example, Aluminum Chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used. As the stabilizer, any one type may be used alone, or two or more types may be used in combination.

[0061] When a stabilizer is added, the amount added is preferably 0.01 to 30% by weight, more preferably 0.05 to 25% by weight, and even more preferably 0.1 to 20% by weight, based on the total weight of the epoxy resin composition.

[0062] Reactive Diluent The epoxy resin composition of the present embodiment may contain a reactive diluent, if desired, to the extent that the effects of the present invention are not impaired. In this specification, the reactive diluent refers to a compound that has one epoxy group (glycidyl group) and has a relatively low viscosity at room temperature. Depending on the purpose, the reactive diluent may have, in addition to the epoxy group, other polymerizable functional groups, such as alkenyl groups such as vinyl and allyl, or unsaturated carboxylic acid residues such as acryloyl and methacryloyl.

[0063] Examples of the reactive diluent include monoepoxide compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, and α-pinene oxide; and monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

[0064] When a reactive diluent is contained, the content thereof is preferably 1 to 150 parts by weight per 100 parts by weight of the epoxy resin.

[0065] Other Additives If desired, the epoxy resin composition of the present embodiment may further contain other additives, such as coupling agents, carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, solvents, etc., within the scope of the present embodiment. The type and amount of each additive are as per usual.

[0066] There are no particular limitations on the method for producing the epoxy resin composition of this embodiment. For example, the epoxy resin composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (C), and, if necessary, other optional components, into an appropriate mixer, and stirring and mixing them while heating to melt them, if necessary, to form a homogeneous composition. The mixer is not particularly limited, and examples of the mixer that can be used include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill, all of which are equipped with a stirrer and a heater. These devices may also be used in appropriate combinations.

[0067] The epoxy resin composition of this embodiment can be a one-component resin composition contained in a single container, or a two-component (or multi-component) resin composition divided into two or more containers, depending on the intended use. When a two-component (or multi-component) resin composition is used, the components (A) to (C) and other optional components as required can be selected in the same manner as for a one-component resin composition. Furthermore, when a two-component (or multi-component) resin composition is used, the components (A) to (C) and other optional components as required can be divided into two or multiple components in any manner without particular limitation. When divided into two or multiple components in any manner, each component may contain one or more components selected from the components (A) to (C) and other optional components as required. Alternatively, the components (A) to (C) and other optional components as required may be contained in a single component. Alternatively, a component may contain only the components (A) to (C) and / or other optional components as required. For example, when separating into liquid A and liquid B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C); liquid A: component (A) and component (B), liquid B: component (C); liquid A: component (A) and component (B), liquid B: component (A) and component (C); liquid A: component (A) and component (B), liquid B: component (B) and component (C); liquid A: component (A) and component (C), liquid B: component (B); liquid A: component (A) and component (C), liquid B: component (B) and component (C). When components (A) to (C) are contained in liquid A, liquid B may contain one or more selected from components (A) to (C). In addition, components other than components (A) to (C) (e.g., thiol compounds other than component (B)) may be contained in both or either of liquid A and liquid B in the above combination. When the components (A) to (C) are contained in Liquid A and the other components are contained in Liquid B, Liquid A alone or a combination of Liquid A and Liquid B can be considered the resin composition of this embodiment. On the other hand, when the components (A) to (C) are contained in separate liquids, the respective liquids can be considered together to be the resin composition of this embodiment.Examples of the case where the components (A) to (C) are contained in separate liquids include a resin composition in which the components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of the components (A) to (C).

[0068] The epoxy resin composition thus obtained is thermosetting, and preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour at a temperature of 100° C. When the epoxy resin composition of the present embodiment is used to manufacture a semiconductor module containing components that deteriorate under high temperature conditions, it is preferable to thermally cure the composition at a temperature of 50 to 90° C. for 30 to 120 minutes.

[0069] The epoxy resin composition of the present embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting semiconductor devices or electronic components or components constituting the same, or as a raw material thereof.

[0070] [Adhesive or Sealant] An adhesive or sealant according to one embodiment of the present invention comprises the epoxy resin composition of the above-described embodiment. This adhesive or sealant provides excellent fixation, bonding, or protection for engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect components constituting a semiconductor device or electronic component. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and time-of-flight sensor modules, semiconductor modules, and integrated circuits.

[0071] The adhesive or sealant of this embodiment can be a one-component adhesive or sealant contained in a single container, or a two-component (or multi-component) adhesive or sealant divided into two or more containers, depending on its intended use. When used as a two-component (or multi-component) adhesive or sealant, the components (A) to (C) and other optional components as needed can be selected in the same way as for the one-component type, and the curing method is also the same as for the one-component type. Furthermore, when used as a two-component (or multi-component) adhesive or sealant, the components (A) to (C) and other optional components as needed can be divided into two or multi-components in any way without particular limitation. When the mixture is separated into two or more liquids by any separation method, each liquid may contain one or more components selected from the components (A) to (C) and other optional components as required, or the components (A) to (C) and other optional components as required may be contained in one liquid, or there may be a liquid consisting only of the components (A) to (C) and / or other optional components as required. For example, when separating into liquid A and liquid B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C); liquid A: component (A) and component (B), liquid B: component (C); liquid A: component (A) and component (B), liquid B: component (A) and component (C); liquid A: component (A) and component (B), liquid B: component (B) and component (C); liquid A: component (A) and component (C), liquid B: component (B); liquid A: component (A) and component (C), liquid B: component (B) and component (C). When components (A) to (C) are contained in liquid A, liquid B may contain one or more selected from components (A) to (C). In addition, components other than components (A) to (C) (e.g., thiol compounds other than component (B)) may be contained in both or either of liquid A and liquid B in the above combination. When components (A) to (C) are contained in liquid A and the other components are contained in liquid B, liquid A alone or a combination of liquid A and liquid B can be considered the adhesive or sealant of this embodiment. On the other hand, when components (A) to (C) are contained in separate liquids, the respective liquids can be considered together to be the adhesive or sealant of this embodiment.Examples of the case where the components (A) to (C) are contained in separate liquids include an adhesive or sealant in which the components (A) to (C) are separated into two or more containers, and specifically, a kit composed of multiple liquids containing any of the components (A) to (C).

[0072] [Cured Product of Resin Composition, Adhesive, or Sealant] A cured product according to one embodiment of the present invention is a cured product obtained by curing the epoxy resin composition, adhesive, or sealant according to the above-described embodiment. Discoloration of an adherend (particularly a metal) to which this cured product is adhered is suppressed.

[0073] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to one embodiment of the present invention includes the cured product according to the above-described embodiment. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and time-of-flight (TOF) sensor modules, other semiconductor modules, and integrated circuits.

[0074] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and percentages are by weight unless otherwise specified.

[0075] [Examples 1-2, Comparative Examples 1-3, Reference Example 1] Epoxy resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in parts by weight (unit: g). The components used in the examples and comparative examples are as follows:

[0076] (A) Epoxy resins with a halogen content of 1600 ppm or less (A-1): YDF-8170 (bisphenol F type liquid epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., total chlorine content: 900 ppm, epoxy equivalent: 159 g / eq) (A-2): jER828EL (bisphenol A type diglycidyl ether, high-purity jER828, manufactured by Mitsubishi Chemical Corporation, total chlorine content: 1430 ppm, epoxy equivalent: 189 g / eq) (A') Epoxy resins with a halogen content of more than 1600 ppm (A'-1): EP-4003S (bisphenol A-PO type, manufactured by ADEKA Corporation, total chlorine content: 1800 ppm, epoxy equivalent: 255 g / eq) (A'-2): EPOX MK R540 (low chlorine product) (diglycidyl ester epoxy resin of hexahydrophthalic anhydride, manufactured by Air Water Inc., total chlorine content: 3000 ppm, epoxy equivalent: 162.5 g / eq) (A'-3): EPOX MK R540 (diglycidyl ester epoxy resin of hexahydrophthalic anhydride, manufactured by Air Water Inc., total chlorine content: 10,000 ppm, epoxy equivalent: 162.5 g / eq) The total chlorine content of the epoxy resin is determined by sample combustion-ion chromatography in accordance with BS EN 14582:2007.

[0077] (B) Thiol compound represented by chemical formula (I) (B-1): Thiol compound represented by chemical formula (I) (1,2,3-(3-mercaptopropyloxy)propane) (obtained from Shikoku Chemical Industry Co., Ltd., thiol equivalent: 106 g / eq). Note that this thiol equivalent is an average value of values ​​measured by a known method, for example, the method disclosed in paragraph

[0079] of JP-A No. 2012-153794. (B') Other thiol compound other than component (B) (B'-1): 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril represented by the following formula (product name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd., thiol equivalent: 110 g / eq).

[0078] (C) Basic Curing Catalyst (C-1): Amine-epoxy adduct latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation) The latent curing catalyst (C-1) is provided in the form of a dispersion (latent curing catalyst / mixture of bisphenol A epoxy resin and bisphenol F epoxy resin=33 / 67 (weight ratio)) in which fine particle latent curing catalyst is dispersed in epoxy resin (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (epoxy equivalent: 180 g / eq)).

[0079] In the examples, comparative examples and reference examples, the properties of the resin compositions were measured as follows.

[0080] [Evaluation of Substrate Discoloration] 0.05 g of each resin composition was applied in a circular pattern to a copper (Cu) substrate and a nickel (Ni) substrate, and the resulting samples were subjected to a thermal curing treatment by heating at 80°C for 60 minutes in a fan dryer to produce cured products on the substrates. The resulting cured samples were then left in a thermo-humidistat chamber at a temperature of 85°C and a relative humidity of 85% for 20 hours. The presence or absence of discoloration on the substrate after 20 hours of standing was visually confirmed. The presence and degree of discoloration were evaluated according to the following criteria. Table 1 shows the measurement results. FIG. 1 is a photograph taken from above of the copper substrate used in the discoloration evaluation of Example 1, Comparative Example 2, and Reference Example 1 after standing for 20 hours in an 85°C / 85% RH environment. The same evaluation was also performed on the two-component resin composition of Example 1, in which Liquid A was component (A) and Liquid B was component (B) and component (C). "-": No discoloration of the substrate was observed. "+": Some discoloration was observed on the substrate. "++": Significant discoloration was observed on the substrate.

[0081]

[0082] Copper substrates coated with the epoxy resin compositions of Examples 1 and 2, each containing an epoxy resin with a halogen content of 1600 ppm or less, showed no discoloration even after standing for 20 hours in an 85°C / 85% RH environment. On the other hand, copper substrates coated with the epoxy resin compositions of Comparative Examples 1 to 3, each containing an epoxy resin with a halogen content exceeding 1600 ppm but not containing an epoxy resin with a halogen content of 1600 ppm or less, showed discoloration after standing for 20 hours in an 85°C / 85% RH environment. The epoxy resin composition of Reference Example 1, which contains a different thiol compound instead of the thiol compound represented by chemical formula (I), did not show any discoloration of the copper substrate after standing for 20 hours in an 85°C / 85% RH environment, even though it contained an epoxy resin with a halogen content exceeding 1600 ppm. This indicates that substrate discoloration is a problem specific to the thiol compound represented by chemical formula (I). Similar results were obtained with nickel substrates as with copper substrates. Although not shown in Table 1, a similar evaluation was also performed on a two-component resin composition in which the composition of Example 1 was changed so that liquid A was the component (A) and liquid B was the component (B) and the component (C), and similar results were obtained.

[0083] The epoxy resin composition of the present invention is extremely useful, for example, as an adhesive or sealant for fixing, joining or protecting semiconductor devices or electronic components or components constituting them, or as a raw material thereof.

[0084] The disclosure of Japanese Patent Application No. 2023-119048 (filing date: July 21, 2023) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. (A) an epoxy resin having a halogen content of 1600 ppm or less; (B) a compound represented by the chemical formula (I): and (C) a basic curing catalyst.

2. The epoxy resin composition according to claim 1, wherein the basic curing catalyst (C) is a thermal latent curing catalyst.

3. The epoxy resin composition according to claim 1 or 2, wherein the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of component (A)] / [number of thiol group equivalents of component (B)]) is 0.1 to 10.

4. The epoxy resin composition according to any one of claims 1 to 3, wherein components (A) to (C) are contained in a single container.

5. The epoxy resin composition according to any one of claims 1 to 3, wherein the components (A) to (C) are separated into two or more containers.

6. An adhesive or sealant comprising the epoxy resin composition according to any one of claims 1 to 5.

7. The adhesive or sealant according to claim 6, which is for use in semiconductor devices or electronic components.

8. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5, or the adhesive or sealant according to claim 6 or 7.

9. A semiconductor device or electronic part comprising the cured product according to claim 8.

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